Seeing that Picture Red has just give me an idea for the next villain.
Kid Buu from DragonBall Z, this guy actually did what most villains say there going to do, destroy the earth. Best of it is he didn't even stall for time or give any warning he just fucking does it.
Edit: Due to a broken picture and the fact that I'm unable to find another one, I'm changing this villain. However Glen Baskerville from Pandora Hearts does get a special mention.
Sosuke Aizen from Bleach. I wasn't going to put this guy in, but after thinking about it, he deserves to be here. Sure he's way to overpowered, but credit to Kubo the way he was introduced was clever.
Hansel and Gretal from Black Lagoon. Just three more villains to go, till I reach 20. Also these two share a spot, considering the fact that they're never apart from each other.
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