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Written by Anonymooo
As the most recent battle for the main character this placement is partially the impact of having just experienced it, but there was so much riding on this fight that it's impossible to ignore. The whole purpose of Ichigo, Chad and Ishida (later joined by Rukia and Renji, and a half-dozen Captains) busting into the Arrancar's home turf Hueco Mundo, was to rescue Inoue Orihime. The road was long and brutal, having had to cut through an army of grotesque hybrids and sadistic lackeys. But just as Ichigo had seemingly rescued Orihime from vicious-yet-honorable Arrancar vanguard Grimmjow, she was whisked away by Ulquiorra, a high-ranking villain we feared and respected at the same time. His dismissive nihilism and casual mutilation of his subordinates and enemies alike had instilled a sense of dread. We knew Ichigo would have to fight him someday, and the results would make us flinch...
When it happened, they most certainly did: a showcase of swordsmanship expertise turned into a shooting gallery of high-powered spiritual energy, with Ichigo running out of stamina while Ulquiorra looked completely unfazed. Once Ichigo activated his trump card, the Hollow Mask and all the additional power it brought him, all hope came crashing down as Ulquiorra then released his true form, Murcielago, and promptly beat Ichigo into paste, effortlessly halting Ichigo's offense and dealing a wound so grave that anybody else but The Hero would sure as hell be dead from it.
But then the miraculous happened: not only did Ichigo survive such grievous injury, but it had unlocked... something within him. This thing, this force of nature completely overtook Ichigo's body, a force so unstoppable that it terrorized the seemingly invincible Ulquiorra, forcing him into a corner and slowly tearing him down piece by piece. And when it was done with him, it caused Ichigo to turn on his allies, trying to keep Ichigo from losing his humanity and turning into the monsters he protects people from. It was an unconventionally dark ending to what seemed like a run-of-the-mill Boss Fight, and for that, Ichigo vs. Ulquiorra will remain memorable.

Jumping back 38 volumes (or 264 episodes--WOW), Ichigo is not a battle-hardened unofficial Captain-Class shinigami but instead a rookie substitute, taking over for Rukia in protecting his town from Hollows. Up to this point Ichigo had made it very clear that he didn't want to fight Hollows: he would only help people and spirits that needed his help right then and there instead of actively hunting them down. It's a reasonable sentiment--why put yourself in harm's way when you don't need to? It's not personal work, especially since Ichigo was just a substitute until Rukia got her powers back. There was no reason for Ichigo to care more than he had to--until the Grand Fisher entered his life again...
Ichigo's mom died when he was very young. This affected his family by forcing his sisters to grow up faster than anyone should ever have to and to top it all off Ichigo blames himself for his mother's death. When he was just a little boy he saw a strangely-dressed kid near a riverbank during a driving rainstorm. He ran to help her and Ichigo's mom followed after him to protect her child. However, the last thing Ichigo remembered of that was his mother lying in a pool of blood, torn open, assuming she'd hit something falling down the hill. It was cold comfort to find out that it wasn't his childish carelessness that caused his mother's death, but a particularly sadistic Hollow.
No fight is as personal to Ichigo as this one. It was a horrible knockdown, drag-out brawl with an inexperienced Ichigo falling prey to mind games and manipulation by the Grand Fisher. His greatest weapon was his anglerfish-like Lure, which was able to mimic the appearance of any of its human victims, including Ichigo's mother. Up to that point, we had never seen a fight so back-and-forth or brutal in Bleach, and the Grand Fisher fight took our breath away with its urgency and emotional weight.

This is the only time that a Bleach supporting cast member has defeated a major, recognized antagonist without any sort of assistance. Let that sink in for a minute: Bleach has a massive cast, with the combat-ready good guys numbering at least three dozen strong counting Ichigo, his friends from Karakura Town, all of Soul Society's Thirteen Court Squads, and now the Vizards...
However, every single time somebody has to fight they end up getting saved by somebody else. The fight continues until either that rescuer gets rescued by somebody else or the original rescuee gets up and finishes the fight. The only real exception to the rule is Ichigo, but he's the main character and is almost always relegated to fighting "boss" characters. Not so in the Soul Society arc: we were presented with twelve boss characters, each with a sub-boss, the both of them being shown as insurmountable odds unless our plucky hometown heroes shaped up.
Shape up they did--Ichigo beats a third-seat and then a Vice Captain with a little elbow grease, but strongman Chad is completely blown out of the water, an unexpected development to really drive home the point of what league a shinigami Captain is in compared to everybody else. So after Ichigo ekes out a draw fighting a particularly menacing Captain (see #2), seeing Ishida and Orihime--two of the considerably weaker members of the group--get ambushed by Captain Kurotsuchi and his Vice Captain/sorta-daughter Nemu, the first thing going through our minds was "They're screwed. Okay, back to Ichigo!"
We couldn't have been more wrong.

Zaraki Kenpachi is a fan-favorite character for many reasons. Chief among those is that he doesn't have any special powers--while other Captains' swords burst into a cloud of razor-sharp sakura petals or extend for miles or set the world on fire, Kenpachi's unique ability (if you can call it that) is to hit people with a sword and cut them in half. That sounds like a damn good power to me, especially in a swordfighting series. Kenpachi's fight with Ichigo is unique in that it's a straightforward brute-force battle, only now Ichigo is showing the experience of fighting with master swordsmen and winning against battle-tested opponents. Ichigo at his then-peak was facing somebody whose only purpose in life had been to get stronger to meet and beat stronger people--it was a match made in heaven.
Well, sort of. Kenpachi was incredibly happy to face Ichigo, who "didn't have time to deal with this" and tried to cut Kenpachi down. Well, Ichigo slammed his sword ineffectively against Kenpachi's body so hard that he hurt his hands.
Then he ran away like a little girl, freaking out about how ridiculously strong Kenpachi was, all while Kenpachi got a good laugh and chased Ichigo through the back alleys of the Soul Society. It's completely understandable: Kenpachi wears bells on his hair so his opponents can hear him coming, and wears an eyepatch to limit his vision so the fight is more challenging (read: fun). Ichigo finally calms down and starts fighting Kenpachi seriously, but this in turn causes Kenpachi to fight seriously, goring Ichigo on his sword and knocking him unconscious.
While bleeding out, Ichigo learns why shinigami treat their swords so well: because zanpakutou, or Soul Cutters, have hearts and minds of their own, and fight alongside their owners to protect them. His sword, Zangetsu, speaks to him and makes him face his inner fears and doubts. Ichigo surpasses them, dragging himself to his feet, flowing not only with his own power, but Zangetsu's as well. Even then, that much sheer power is only enough to earn a draw against the mighty Kenpachi, as both of them collapse in a heap after the gut-wrenching duel.
Most Bleach fights don't go out of their way to be choreographed--it's a back and forth show of force which ends with an ultimate attack finishing the loser. However, Ichigo vs. Kenpachi not only showed how much Ichigo had grown up to that point in terms of experience and fighting prowess, but it showed off exciting swordsmanship that was a test of skill, will, and heart. It was the Rocky line all over again: "it's not about how hard you can hit; it's about how hard you can get hit and keep going!"

Does it make sense for a collection of four fights to be #1 on this list? It does when they all pretty much take place at the same time. Ichigo and company's invasion of the Soul Society has shaken the organization to its core, unveiling a major conspiracy that has resulted in the death of a Captain and the shinigami's leaders to turn on one another. The act that started the series--Kuchiki Rukia transferring her powers to a human, Ichigo--has been branded a capital crime punishable by death. Her brother Byakuya, the man who wiped the floor with Ichigo and brought Rukia back to the Soul Society to face justice, has coldly watched his sister be carried to the chopping block, apathetic to her plight. All hell breaks loose as Ichigo himself crashes the execution, destroying the sentient weapon that would have obliterated Rukia while Kenpachi--in defense of Ichigo's friends thanks to his newfound respect of Ichigo--faces off against two Captains in Bleach's most intelligent and creative fight.
While all that's going on two Captains, convinced that executing Rukia is wrong, had sabotaged the execution and are challenged by the Captain Commander, leader of the 13 Court Squads Yamamoto Genryuusai Shigekuni. The fight is brief and how it plays out is never seen besides the initial clash, but it's a great lead-in to another fight that's happening simultaneously, another fight with a lot of messy personal history involved.
2nd-Divison Captain Soifon is faced with her mentor, Yoruichi, who has been integral in not only helping Ichigo and his friends break into the Soul Society, but halting Rukia's execution and helping Ichigo in obtaining Ban Kai so he can fight on an even keel with the strongest Captains. Soifon is heartbroken that the woman she idolized would be helping intruders and defying Soul Society's establishment, but Yoruichi is able to win her over by showing her superiority. With the battle over, Soifon is overwhelmed with emotion, asking why Yoruichi didn't bring her along when she left Soul Society.
With the old pair reunited, we're brought back to the scene of Rukia's would-be execution, where Ichigo has curbstomped a half-dozen shinigami Vice Captains without even drawing his sword, and has met Rukia's brother Byakuya in single combat. The duel almost claims Ichigo's life as Byakuya unleashes his Ban Kai, laying waste to the landscape. Ichigo finally releases his Ban Kai, and the two fight to a standstill until a freak appearance by an old face inside Ichigo turns the tide. Ichigo resists this strange apparition and, now lucid, suggests to Byakuya that they put all their effort into a single blow that will decide the fight. They clash, and Ichigo comes out on top with a little luck. Normally, this is where the story would end, but oh no, there's lots more.
The conspiracy tearing the Soul Society apart from the inside is thrown into the spotlight, with the head conspirator shocking everybody, and tearing through everybody who dares to stand in his way--even Ichigo. As he brings his conspirators with him, he escapes to Hueco Mundo, the world of the shinigami's eternal enemies, and swears to tear down the foundations of Soul Society and the material world, opening up a grander conflict for the characters of Bleach, a conflict that is only now coming to a head.

Zanpakutō (斬魄刀) is the main weapon of the Shinigami, the Arrancar and the Vizard.
Shikai (始解 - meaning "first release") is the second form available to a Zanpakutō. To activate it, the Shinigami needs to learn the name of their Zanpakutō, which is no easy task as they must mesh their spiritual energy with the Zanpakutō itself.
Bankai (卍解 - meaning "final release") is the second and final stage to a Zanpakutō. To achieve Bankai, the wielder needs to summon the Zanpakutō's spirit into the physical world, which usually takes 10 years or more to achieve.
(c) Tite Kubo/Shueisha, TV TOKYO, dentsu, Pierrot
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