Many characters are unlocked by playing specific quests within the story mode. Many of these quests are unlocked during or after the completion of Chapter 6, with the exclusion of Meng Huo.

Unlockable	How to unlock
Diao Chan	Clear "Battle of Hu Lao Gate" 5-Star Version
Dong Zhuo	Clear "Battle of Luo Yang" and "Battle of Mei Castle" 5-Star Versions
Lu Bu	Clear Chapter 6 of Any Story Mode.
Meng Huo	Clear "Unification of Nan Zhong" (Unlocked By Clearing the Previous Two Nanman Quests Given by the "Second Gatekeeper" in Chapter 3)
Yuan Shao	Clear "Zenith Tower" Request Mission
Zhang Jiao	Clear "Yellow Turban Rebellion" 5-Star Version