Brains
Alakazam (Pokemon, dude has like 1000 IQ), Myles "Tails" Prower (Sonic)

Brawn
Cloud (Kingdom Hearts Series), Ganondorf (Legend of Zelda)

Gunner
Miss Fortune (League of Legends), Snake (Super Smash Bros Brawl)

Agile
Fox (Starfox), Pit (Kid Icarus)

Leader
Marth (Fire Emblem)

Boss
Bowser (Mario series)

Comedic Relief
GlaDOS/Wheatley (Portal)