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Hancock uses her powers and beauty to make Psykos hesitate in attacking, and then proceeds to one-shot with Mero Mero Mellow, or Slave Arrow. Psykos' intelligence doesn't factor in when she has no clue about her opponent, and her tendency to be easily angered will work in Hancock's favor.

Hancock also has pre-cog and stats amp. She also has her snake Salome to support her in combat. She has durability negation with her physical attacks. Psykos may have Telekinesis, but it will not result in instant victory, whereas a single slave arrow will Petrify Psykos instantly.

Boa Hancock wins.
 
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