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Hmmm, thos is actually hard. Most don't make much of a mark when I think about it. For instance Far Cry, which often sells itself on its villians, they are still rather one-note and annoying rather than memorable (admittedly haven't played 3).

First one that springs to mind is the Joker in Arkham City.

Most of my favourite games - AC 2, RDR 2, God of War, Halo etc - the villians are more there as obstacles, they aren't really what I remember the games for. Halo, for instance the Covenant is memorable but I'm more think of an individual rather than factions.