90. Gary Oak - Pokemon
It may seem a little mean to call Gary a villain, especially seeing as he is only trying to become the very best as all Pokemon Trainers should, but then he's a bit of a bully, always popping up to start a fight with you, no matter how many times he loses. Annoyingly Gary is always one step ahead, even becoming to Pokemon League Champion before you and eventually becoming your final test.
89. Leorina - Klonoa 2: Lunatea's Veil
Leorina was an ex priestess-in-training who desired the power of the gods, she became a sky pirate in the hopes of uncovering the Kingdom of Sorrow so that the whole world would share in her depression. After doing so, she was consumed by the sorrow and transformed into a large monster, changing her ways and helping Klonoa stop the King of Sorrow once she had been defeated.
88. Rufus Shinra - Final Fantasy VII
Rufus became President of Shinra after his father's murder at the hands of Sephiroth early in Final Fantasy VII and was notable for his plan to control the people of Midgar using fear alone. During his fight with Cloud, Rufus is strong enough to fire his shotgun with one hand and his escape, holding onto the skids of a helicopter, is effortlessly cool, as is his supposed demise, facing down a blast from Diamond Weapon with no fear.
87. Colonel Mael Radec - Killzone 2
Radec was the bodyguard of Scolar Visari, as well as the leader of the Helghast forces that defended Pyrrhus City. An incredibly dangerous adversary, Radec even succeeded in killing Jan Templar, before eventually maintaining his honour by killing himself after he is mortally injured in battle. Oh, and he could turn invisible when you were fighting him, making his boss battle incredibly difficult.
86. Dr. Killjoy - The Suffering
Dr. Killjoy is a large part of what made The Suffering such an interesting and exciting game to play. A deceased and very depraved psychologist and doctor who worked at the Asylum, he would often use horrific methods on his patients, usually killing them. In the game he appears via old film projectors, and a memorable boss battle requires Torque to destroy numerous projectors to survive.