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Who is the woman with long black hair staring at Luffy in the opening sequence starting around episode 400?

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That is Boa Hancock. She is one of the Shichibukai and the appearance that you are referring to is currently her only anime appearance. She makes her debut in the next arc, so she'll be showing up pretty soon. If you can't wait, then you can read the manga. She first appears in chapter 515.

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