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Yoruichi is the fastest of the Shinigami, she the "Goddess of Flash Steps", and the fastest Arrancar is Zommari Leroux, the Septima Espada

I believe the fastest is now the fully evoved Aizen as he was able to Yoruichi, Isshin, and Uahara off guard and defeat them. But then Ichigo can use flashstep and create after images

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