[collapse=How to Unlock]
Jigglypuff: Beat Classic or Adventure Mode with any one character or play 25 VS. matches.
Luigi: Complete Stage #1 of Adventure Mode with the time ending in a "2" in the second's slot, then beat Luigi in less than a minute or play 50 VS. matches.
Captain Falcon: Beat Classic Mode in under 20 Minutes (original way to unlock him in SSB64) or play 75 VS. matches.
Ness: Beat Classic Mode on Normal Difficulty, 3 stock, no continues or reflect 5 projectiles (both are previous ways he was unlocked in an SSB game).
Falco: Beat the 100-Man battle option (how he was unlocked in Melee and Brawl) or play 100 VS. matches.
Ganondorf: Beat Classic Mode on Hard Difficulty with Link or Zelda or play 125 VS. matches.
Marth: Play Classic Mode with all eight regular characters or use them in VS. mode (how he was unlocked in Melee) or play 150 VS. matches.
Sonic: Beat Classic Mode in under 10 Minutes or play 175 VS. matches.
Ice Climbers: Win a team match or play 200 VS. matches.
Bowser: Beat Classic or Adventure Mode with Mario or Luigi and without using a continue or play 225 VS. matches.
Metaknight: K.O. an opponent in less than 30 seconds or play 250 VS. matches.
Diddy Kong: Bury an opponent 5 times or play 275 VS. matches. (Since tripping is gone, I figured being buried is the closest thing)
Pokemon Trainer: Transform 5 times or play 300 VS. matches.
Zelda/Shiek: Transform 15 times or play 325 VS. matches.
Captain Olimar: Collect 50 pieces of food or play 350 VS. matches.
Snake: K.O. an opponent with an explosive 10 times or play 375 VS. matches.
Ike: Complete Classic or Adventure Mode with Marth and without continuing (how Roy was unlocked in Melee) or play 400 VS. matches.
Peach: Play 15 matches on Mushroom Kingdom or play 425 VS. matches.
Saki: K.O. an opponent 10 times with a Ray Gun/Super Scope/Beam Sword, use Assist Trophies 10 times or play 450 VS. matches.
Wario: Beat Classic Mode on Hard Difficulty with Mario or play 475 Vs. matches.
King DeDeDe: Swallow an opponent 10 times or play 500 VS. matches.
Ridley: Play Giant Battle Mode (in Special Modes) 15 times or play 525 VS. matches. (Yes, this is a too big joke.)
Wolf: Beat him in Boss Battle Mode with Fox or Falco or play 550 VS. matches.
Midna & Wolf Link: Beat Classic Mode on Hard difficulty with Ganondorf or play 575 VS. matches.
Waluigi: Beat Classic Mode on Hard Difficulty with Luigi or play 600 VS. matches.
Megaman: K.O. an opponent 15 times with a projectile or play 625 VS. matches.
Isaac: Bury an opponent 25 times, use Assist Trophies 25 times or play 650 VS. matches.
Lucario: K.O. an opponent with more than 150% 15 times or play 675 VS. matches.
Wii Fit Trainer: "Gracefully" dodge an opponent's attack 15 times or play 700 VS. matches.
Ghirahim: K.O. an opponent "beautifully" (star K.O.s) 25 times or play 725 VS. matches.
Bowser Jr. & Shadow Mario: Grab Peach 25 times as Bowser or play 750 VS. matches.
Andy: K.O. an opponent 25 times with explosives, use Assist Trophies 50 times or play 775 VS. matches.
Villager: Collect 250 different trophies (This was ROB's way to be unlocked in Brawl, but collecting is the Villager's thing), pick up an item 250 times or play 800 VS. matches.
Masked Man: Absorb a total of 300% using Ness' PSI Shield or play 825 VS. matches.
Mewtwo: Play for a total of 20 hours in VS. Mode or play 850 VS. matches.
Chrom: Win a Team Match as or VS. Ike & Marth or play 875 VS. matches.
Tingle: Take a total of 25 screenshots or play 900 VS. matches. (If you get this, you're awesome.)
Little Mac: K.O. an opponent 25 times with a punch or play 925 VS. matches.
Pac-Man: Use the power of a Star 25 times or play 950 VS. matches. (It's a power pellet reference)
Ray: K.O. an opponent 50 times using a Ray Gun/Super Scope, use Assist Trophies 75 times or play 975 VS. matches.
Robin: K.O. an opponent with magic or swords 50 times or play 1000 VS. matches.
Mr. Game And Watch: Can only be unlocked after unlocking all other characters and beating All Star Mode.