Mad Hatter, aka Jervis Tetch, may not be well known in the Villain circle, but be does fit in well.
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batman
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This Batman Villains photo contains
snap brim hat, boater, leghorn, panama, panama hat, sailor, skimmer, straw hat, and campaign hat.
There might also be
pith hat, pith helmet, sun helmet, topee, topi, cavalier hat, and slouch hat.