On the Marvel End there have been a crazy amount. Deadly Foes of Spider-Man/Lethal Foes of Spider-Man were pretty much villain books. Sabretooth had a few mini series, Kingpin had a 7 issue one, Typhoid Mary had 4, Nightmare 4, Bullseye has had a couple of mini-series and Dark Reign had a ton, Dark Avengers/Dark Hawkeye/Spider-man. Mr. Negative, Lethal Legion, The Hood. Marvel is coming out with Villains for Hire next month. Loki had a few mini-series and one-shots. Super Villain Team-Up Modok's 11 starred a bunch of villains. I guess you could include Thunderbolts too. Deadpool first 2 mini-series originally I guess you could say were villain books. Baron Zemo had a 4 issue mini-series a few years back.