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The latter is exactly what happened when Szayelaporro fought against Uryuu, Renji, Pesche, and Dondochakka.
When the last ditch attack failed, it seemed as if all was lost. Not only are the two very intelligent, they are also very confident in themselves, and that's what truly makes this an exciting fight.
In the end, it's Mayuri whose confidence is well-deserved.
After toying with Szayelaporro, Mayuri shows that he is the smartest by constantly being one step ahead of his opponent and always prepared for the unknown.
After coming to the terms with the fact that he needs to learn how to control his inner hollow, Ichigo seeks out the Vizard hoping that they will teach him how to do so.
After realizing that if he were to continue the fight as it was going he would die, Kenpachi decides to bring out the most secret of techniques: Kendo.
Following the way of the sword, and gripping the sword with both hands, Kenpachi is able to fall his formidable foe in one swing of his sword.
Even when Szayelaporro reveals that he's virtually immortal, Mayuri remains unphased, as ends the fight in perhaps one of the most brutal ways in all of Bleach.
This fight makes the list because of how often it ebbs and flows (pun intended) in the favor of Hitsugaya and Harribel.