Shu

Zhao Yun - Initially available
Guan Yu - Initially available
Zhang Fei - Initially available
Zhuge Liang - Clear Musou Mode with 1 Shu character.
Liu Bei - Clear Musou Mode with 3 Shu characters.
Ma Chao - Han Zhong Attact Defense Battle (Wei scenario), succeed 2 battle objectives.
Huang Zhong - Battle of Mt. Ding Jun (Wei scenario), succeed 1 battle objective.
Wei Yan - Battle of Wu Zhang Plains (Shu scenario), succeed 2 battle objectives and clear battle with Wei Yan alive.
Guan Ping - Battle of Fan Castle (Shu scenario), succeed 2 battle objectives and clear battle with Guan Ping alive.
Pang Tong - Cheng Du Suppression Battle (Shu scenario), succeed 3 battle objectives and clear battle with Pang Tong alive.
Yue Ying - Battle of Wu Zhang Plains (Wei scenario), succeed 1 battle objective.

Wei

Xiahou Dun - Initially available
Dian Wei - Initially available
Sima Yi - Initially available
Zhang Liao - Clear Musou Mode with 1 Wei character.
Cao Cao - Clear Musou Moce with 3 Wei characters.
Xu Zhu - Battle of He Fei (Wu scenario), defeat Cao Ren and Xu Zhu under 10 minutes.
Xiahou Yuan - Battle of Mt. Ding Jun (Shu scenario), succeed 1 battle objective.
Xu Huang - Battle of Fan Castle (Wei / Wu scenario), succeed 2 battle objectives.
Zhang He - Han Zhong Attack Defense Battle (Shu scenario), succeed 2 battle objectives.
Cao Pi - Battle of He Fei (Wu scenario), defeat Cao Pi in 5 minutes.
Cao Ren - Battle of Fan Castle (Lu Bu scenario), succeed 2 battle objectives.
Zhen Ji - Xu Chang Invasion Battle (Lu Bu scenario), succeed 1 battle objective.

Wu

Zhou Yu - Initially available
Lu Xun - Initially available
Sun Shang Xiang - Initially available
Gan Ning - Clear Musou Mode with 1 Wu character.
Sun Jian - Clear Musou Mode with 3 Wu characters.
Taishi Ci - Wu County Settlement Battle (Wu scenario), defeat Taishi Ci.
Lu Meng - Battle of He Fei (Wei scenario), succeed 2 battle objectives.
Huang Gai - Battle of Chi Bi (Wu scenario), succeed 3 battle objectives including the fire attack.
Zhou Tai - Battle of Yi Ling (Shu scenario), succeed 3 battle objectives.
Sun Ce - Battle of Xia Pi (Wu scenario), clear battle with Sun Ce alive.
Sun Quan - Battle of Chi Bi (Lu Bu scenario), defeat Cao Cao and Sun Quan in 10 minutes.
Ling Tong - Battle of Shi Ting (Wei scenario), defeat Xiao Qiao, Gan Ning and Ling Tong.
Xiao Qiao - Battle of Shi Ting (Wu scenario), succeed 3 battle objectives.

Others

Lu Bu - Clear Musou Mode with Liu Bei, Cao Cao and Sun Jian.
Diao Chan - Clear Musou Mode with 1 character from each of the 3 kingdoms.
Dong Zhuo - Clear Musou Mode with Lu Bu.
Yuan Shao - Battle of Guan Du (Cao Cao scenario), succeed 3 battle objectives.
Zhang Jiao - Yellow Turban Rebellion (Allied Army scenario), succeed 3 battle objectives.