| Character | How to unlock |
| Ace | Complete the Story Mode with two different characters.
|
| Blackbeard | Complete the Story Mode with Shanks.
|
| Crocodile | Complete the Story Mode with three different characters.
|
| Ener | Complete the Story Mode with five different characters.
|
| Mihawk | Complete the Story Mode with all other characters.
|
| Shanks | Complete the Story Mode with Mihawk.
|
| Smoker | Complete the Story Mode with one character.
|
| Vivi | Complete the Story Mode with four different characters.
|
