There are a few ways in which you can unlock each character, though every character can be unlocked by completing a certain number of Brawl matches and then defeating the unlocked character in a 1v1 match.
Defeat Captain Falcon after playing at least 70 Brawl matches. Defeat Captain Falcon after completing Classic Mode on Normal (or higher) in under 12 minutes. Get Captain Falcon to join your Subspace Emissary (Stage 20).
Defeat Falco after playing at least 50 Brawl matches. Defeat Falco after finishing a 100-Man Brawl. Get Falco to join your Subspace Emissary (Stage 18).
Defeat Ganondorf after playing at least 200 Brawl matches. Defeat Ganondorf after using Zelda to complete Classic Mode on Normal difficulty. Defeat Ganondorf after using Link to complete Classic Mode on Hard difficulty. Get Ganondorf to join your Subspace Emissary (Stage 30). [1] X Research source
Defeat Jigglypuff after playing 350 Brawl matches. Defeat Jigglypuff after completing the Subspace Emissary and Classic Mode with any character except Ike. [2] X Research source Defeat Jigglypuff by using a blast after completing the Subspace Emissary and completing all even matches through Stage 20. Defeat Jigglypuff after completing the Subspace Emissary, returning to Stage 18 (“The Swamp”), firing yourself from one of the barrels into a floating door, and finding Jigglypuff there.
Defeat Lucario after playing at least 100 matches in Brawl mode. Defeat Lucario after beating Target Smash on each difficulty. Get Lucario to join your Subspace Emissary (Stage 21).
Defeat Luigi after playing 22 matches in Brawl mode. Finish the “Classic” mode without losing (e. g. , no Continues), then defeat Luigi. Get Luigi to join your Subspace Emissary (Stage 29). Select Link in classic and beat it to unlock Capt. Falcon, Ness, or Marth (beat them), then select Mario and finish Classic mode. Luigi will challenge you.
Defeat Marth after playing at least 10 Brawl matches. Defeat Marth after completing Classic Mode at least once. Get Marth to join your Subspace Emissary (Stage 8).
Defeat Mr. Game & Watch after playing at least 250 Brawl matches. Complete Classic Mode with each stock character. Defeat Mr. Game & Watch after completing Target Smash on any on difficulty level with at least 30 distinct characters. Get Mr. Game & Watch to join your Subspace Emissary (Stage 25).
Defeat Ness after reflecting 10 projectiles. Defeat Ness after playing 5 Brawl matches. Get Ness to join your Subspace Emissary (Stage 29).
Play at least 160 Brawl matches, then defeat R. O. B. Defeat R. O. B after obtaining 250 trophies. Get R. O. B to join your Subspace Emissary (Stage 27).
Defeat Snake after playing at least 130 Brawl matches. Defeat Snake after playing at least 15 matches on Shadow Moses Island. Get Snake to join your Subspace Emissary (Stage 23).
Defeat Sonic after playing at least 300 Brawl matches. Complete the Subspace Emissary. Defeat Sonic after completing Classic Mode with 10 separate characters. Play at least 10 hours of VS mode.
Defeat Toon Link after playing at least 400 Brawl matches. Complete the Subspace Emissary. After that, find Toon Link behind the first door in Stage 9 (“The Forest”), then defeat him. Defeat Toon Link in Brawl mode after completing both the Subspace Emissary and Classic Mode.
Defeat Wolf after playing at least 450 matches in Brawl mode. Complete the Subspace Emissary. After that, use fox to beat Boss Rush, then defeat Wolf. On Stage 14 (“The Ruins”), play as fox, jump onto the platform at the end of the second part of the stage and ride it down until you fall, then defeat Wolf on the other side of the door.
