Contains Spoilers!!!
There are more than 35 characters in the Super Smash Bros Brawl Roster, some with alternate forms (marked with an *) They are the following:
Newcomers
Pit
Wario (Both Warioware and Overalls Wario)
Ike
Pokemon trainer*
Diddy Kong
Meta Knight
Snake
Lucas
Sonic
King Dedede
Pikmin and Olimar
Veteran Fighters
Mario
Link
Kirby
Pikachu
Fox
Samus*
Zelda*
Bowser
Donkey Kong
Ice Climbers
Yoshi
Peach
Secret Characters
Ness
Luigi
Ganondorf
Toon Link (Wind Wakers Link, newcomer)
R.O.B. (newcomer)
Falco
Wolf (newcomer)
Captain Falcon
Lucario (newcomer)
Jigglypuff
Marth
Mr. Game & Watch
Black Shadow (rumor)
Transformations
Sheik (Zelda)
Zero Suit Samus (Samus Aran)
Squirtle/Ivysaur/Charizard (Pokémon Trainer)
Note: *Secret Characters are both new and veterans