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Team Plasma by themselves were never that impressive. Everything relating to N and Ghetsis was. I even go so far as to say that Ghetsis was so much of a magnificent bastard that his original plan should've worked, just that he didn't count on the protagonist being that strong. I will say this makes him the best villain the MAIN series has known, at least until he became ordinary in BW2. The first matter still counts, though. Otherwise, there are antagonists that outrank everything that the main series villains ever did in the spinoffs. My personal top is the Societea from Guardian Signs. When you blow up a flipping island, you immediately have my attention.