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In Episode 470, Luffy feels as if both his hands got cut by Mihawk's sword. And then immediatly after that, feeling he stopped that attack.

So, is it possible that it was the first time Luffy had experienced/activated the Kenbunshoku Haki?

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    It might be, but it was never confirmed. Mihawk just called Luffy "clearheaded", but in retrospect there is a big probability of it being Haki.
    – Peter Raeves
    Oct 6, 2015 at 14:56

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From the One Piece Wikia article on Kenbunshoku Haki:

The first time it was seen being used and referred to as Haki was during Luffy's battle on Amazon Lily with the Boa Sisters. Later, Rayleigh explained Haki to Luffy and confirmed that "Mantra" is the Skypiean name for the ability.

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