Secrets
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Dr. Mario
To unlock Dr. Mario, you must complete 1-P Classic Mode using Mario at any difficulty/stock and without continuing.
Pichu
To unlock Pichu, complete Event 37 (Legendary Pokemon). Pichu will challenge you; win and you'll be able to play as Pichu!
Roy
To unlock Roy, also from the Fire Emblem series, complete Adventure Mode using Marth at any difficulty/stock. Roy will challenge you; defeat him and you can play as him.
Mr. Game & Watch
To unlock Mr. Game & Watch, you must complete either Classic or Adventure 1-P mode with ALL characters at any difficulty/stock, regular and hidden (that includes Mewtwo). After you do that, you'll be challenged; win this battle and you can play as Mr. Game & Watch!
Youge Link
To unlock Young Link, complete Classic mode with 10 different characters at any difficulty/stock (2 of those characters must be Link and Zelda). You'll then be challenged by Young Link; defeat him to be able to play as him in the game!
Mewtwo
To unlock Mewtwo, play in VS. Mode for either 20 hours (Combined VS. Play Time total), or play 700 matches (without quitting) in that mode. After either requirement is met, Mewtwo will challenge you; beat him and you can play as Mewtwo!
Marth
To unlock Marth from the Fire Emblem series, complete Classic mode with all 14 regular characters (not ones you've unlocked). Marth will then challenge you; beat him to gain him as a selectable character. Or you can alternatively, you can simply use every character as a human player in VS. Mode, and get a challenge from Marth that way.
Luigi
To unlock Luigi, in Adventure Mode, complete the stage with a 2 in the seconds meter (03:12:43 for example). You'll then view a scene where Luigi comes and kicks Mario away so he can fight you with Peach. Defeat them both, then go on and complete Adventure Mode. You'll have to fight Luigi; defeat him and you can play as him.
Jigglypuff
To unlock Jigglypuff, simply complete the game in 1-P Mode at any difficulty/stock (Adventure or Classic
Ganondorf
To unlock the evil Ganondorf, complete Event 29. You will then be challenged by Ganondorf; defeat him and you can play as him from then on.
Falco
To unlock Falco, you must complete the 100-Man Melee mode. Defeat Falco after you complete that, and you can play as him.
More secrets coming soon