To unlock characters you can play a certain amount of Smash matches. After you've played the required amount of Smash matches a challenger will appear, defeat that challenger in order to unlock the character.
Character | How to unlock
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Bowser Jr. | Play 100 Smash matches or beat Classic Mode on Normal difficulty as Bowser.
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Dark Pit | Play 50 Smash matches or beat Classic Mode on 5.0 difficulty.
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Dr. Mario | Play 60 Smash matches or beat Classic Mode on Normal difficulty as Mario.
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Duck Hunt | Play 110 Smash matches or beat Classic Mode on Normal difficulty as Luigi.
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Falco | Play 20 Smash matches or beat Classic Mode 1 time.
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Ganondorf | Play 80 Smash matches or beat Classic Mode on Normal difficulty with Link.
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Jigglypuff | Play 120 Smash matches.
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Lucina | Play 40 Smash matches or beat Classic Mode on Normal difficulty with Marth.
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Mr. Game & Watch | Play 90 Smash matches.
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Ness | Play 10 Smash matches.
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R.O.B | Play 70 Smash matches.
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Wario | Play 30 Smash matches or beat 100 Man Battle.
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