| Tristan Taylor | 1 | | |
| Tea Gardner | 1 | Fairy | |
| Yugi Muto | 1 | Dark Magician | |
| Joey Wheeler | 1 | Red Eyes | |
| Bakura Ryou | 1 | Zombie | |
| Espa Roba | 2 | Machine | Defeat all Tier 1 duelists 2 times. |
| Mako Tsunami | 2 | Umi | Defeat all Tier 1 duelists 2 times. |
| Rex Raptor | 2 | Dinosaur | Defeat all Tier 1 duelists 2 times. |
| Weevil Underwood | 2 | Insect | Defeat all Tier 1 duelists 2 times. |
| Mai Valentine | 2 | Harpie/Winged Beast | Defeat all Tier 1 duelists 2 times. |
| Umbra & Lumis | 3 | Trap | Defeat all Tier 2 duelists 3 times. |
| Arkana | 3 | Dark Magician | Defeat all Tier 2 duelists 3 times. |
| Rare Hunter | 3 | Exodia | Defeat all Tier 2 duelists 3 times. |
| Strings | 3 | | Defeat all Tier 2 duelists 3 times. |
| Marik Ishtar | 3 | Discard | Defeat all Tier 2 duelists 3 times. |
| Yami Bakura | 4 | | Defeat all Tier 3 duelists 4 times. |
| Ishizu Ishtar | 4 | Light | Defeat all Tier 3 duelists 4 times. |
| Kaiba Seto | 4 | Blue Eyes | Defeat all Tier 3 duelists 4 times. |
| Shadi | 4 | Ancient | Defeat all Tier 3 duelists 4 times. |
| Yami Yugi | 4 | Dark Magician | Defeat all Tier 3 duelists 4 times. |
| Maximillion Pegasus | 5 | Toon | Defeat all Tier 4 duelists 5 times. Unlocked by obtaining Toon World. |
| Simon | 5 | | Defeat all Tier 4 duelists 5 times. Unlocked by winning the National Tournament held in November. |
| Duel Computer | 5 | Control | Defeat all Tier 4 duelists 5 times. |
| Trusdale | 5 | Exodia | Defeat all Tier 4 duelists 5 times. Unlocked after defeating Simon once or by collecting each of the 819 cards in the game. |