The Super Smash Bros Brawl character list includes:

Bowser
Captain Falcon (Star Fox, unlockable)
Diddy Kong
Donkey Kong
Falco (Star Fox, unlockable)
Fox (Star Fox)
Ganondorf (unlockable)
Ice Climbers
Ike (Fire Emblem)
Jigglypuff (unlockable)
King Dedede (Kirby)
Kirby
Link
Lucario (Pokemon, unlockable)
Lucas (Earthbound)
Luigi (unlockable)
Mario
Marth (Fire Emblem, unlockable)
Meta Knight (Kirby)
Mr. Game & Watch (unlockable)
Ness (Earthbound, unlockable)
Peach
Pikachu
Pikmin
Pit (Kid Icarus)
Pokemon Trainer
Olimar (Pikmin)
R.O.B. (unlockable)
Samus
Sheik (Zelda)
Snake (Metal Gear, unlockable)
Sonic (unlockable)
Toon Link (unlockable)
Wario
Wolf (Star Fox, unlockable)
Yoshi
Zelda
Zero Suit Samus

A screenshot of the starting character screen is below.