First, I'll say how to start out as Zero Suit Samus instead of Samus. When you're at the
character screen, select Samus. With the Wii-Remote, hold Minus and press Plus as you hold
Minus. Let go and enter the fight, you will start as ZSS (Zero Suit Samus.) If you're
using the Wii-Remote and Nunchuck, hold Nunchuck Z and and press Plus. With a Classic
controller, hold R and press Plus. Finally, with a GameCube controller, hold R and press
Start.


Captain Falcon: Successfully complete Classic mode on the Normal or higher difficulty in
under twelve minutes, then defeat Captain Falcon in the next match. Alternately, play 70
offline Brawl matches or have Captain Falcon join you in SSE (Subspace Emissary) mode.


Falco: Successfully complete the 100-Man Brawl. Alternately, play 50 offline Brawl matches
or have Falco join you in SSE mode.


Ganondorf: Successfully complete Classic mode on the Hard difficulty with Link or Zelda.
Alternately, play 200 offline Brawl matches or have Ganondorf join you in SSE mode by
collecting the Zelda and Link trophies.


Jigglypuff: Successfully complete SSE mode, and have Jigglypuff join you in SSE mode by
going to "The Swamp" on the map. Go to near the end (which is basically after you defeat
giant Diddy Kong.) The cannons will shoot you, and you will see a door while being shot.
Swim back to the door, and fight Jigglypuff. Alternately, successfully complete SSE mode,
then complete Event Matches #1 through #20 or play 350 offline Brawl matches.


Lucario: Defeat Lucario in SSE mode with Meta Knight in the Glacial Peak level.
Alternately, successfully complete all five Target Tests with any character or play 100
offline Brawl matches.


Luigi: Successfully complete Classic mode on the Easy difficulty without using any
continues. Alternately, play 22 offline Brawl matches or defeat Luigi in SSE (Subspace
Emissary) mode.


Marth: Successfully complete Classic mode. Alternately, play 10 Brawls or unlock Marth in
SSE mode.


Mr. Game & Watch: Successfully complete all Target Tests on the same difficulty with 30
different characters. Alternately, play 250 offline Brawl matches or have Mr. Game & Watch
join you in SSE mode.


Ness: Play 5 offline Brawl matches. Alternately, reflect ten projectiles or defeat Ness in
SSE (Subspace Emissary) mode.


R.O.B. the robot: Play 160 offline Brawl matches. Alternately, get 250 different trophies
or have R.O.B. join you in SSE mode.


Snake: Play fifteen matches on the Shadow Moses Island stage. Alternately, play 130
offline Brawl matches or have Snake join you in SSE mode in the Battleship Halberd
Interior level.


Sonic: Successfully complete Classic mode with 10 characters. Alternately, play 300
offline Brawl matches or have Sonic join you in SSE mode. When you are about to fight
Tabuu in SSE mode, Sonic will appear. After defeating Tabuu and saving your game, Sonic
will be unlocked.


Toon Link: Successfully complete SSE mode, and have Toon Link join you in SSE mode by
going to "The Forest" on the map. Then, look for the first door near the beginning.
Alternately, successfully complete SSE mode, then complete Classic mode or play 400
offline Brawl matches.


Wolf O'Donnell (Wolf): Successfully complete SSE mode, then complete Boss Battle mode with
Fox or Falco. Defeat Wolf after he challenges you to unlock him. Alternately, play 450
offline Brawl matches, then defeat Wolf after he challenges you. Another method is to
successfully complete SSE mode, and have Wolf join you in SSE mode by going to "The
Ruins". After you get lowered in the pit, you will see a floating door. Go in, then out.
You will now be dropped where the door will be.


Playing 450 offline matches will automatically unlock all characters (if you defeat them
that is.)

A special thanks to http://www.cheatcc.com/ for helping me make this.