Collect the indicated number of Berries in Fighting or Gamble mode. Highlight the silhouette of a character in Fighting or Gamble mode, then press Circle to unlock them.

Ace: 200 Million Berries
Ao Kiji: 250 Million Berries
Crocodile: 81 Million Berries
Enel: 150 Million Berries
Franky: 300 Million Berries
Smoker: 120 Million Berries