Taigong Wang, also known as Jiang Ziya, was a legendary military strategist and the most famous Prime Minister from the Zhou Dynasty of China. He is the one who can easily outmatch Da Ji's strategic thinking and ordered her execution personally in their own world. He has a rather cocky and egotistic personality. He uses a fishing rod as a weapon.
Kiyomori Taira was a military general from the Heian Period of Japan. He is allied with Orochi and is part of his resurrection. He uses a set of gigantic prayer beads as a weapon.
Yoshitsune Minamoto was another military general from the Heian Period, opposing Kiyomori. He can fight Lu Bu evenly match and even unscathed, which surprised Wu. He wields a lightsaber-like gauntlet that is attached to his arm and can fire energy projectiles with it. He is a rather typical samurai.
Himiko was the ancient Japanese shaman queen known for her relationship with the Kingdom of Wei of China. She utilizes a set of energy-firing Dogu dolls. She has a sister-like relationship with Da Ji and both are very protective of each other.
Orochi X (Shin Orochi in Japanese version) is the revived form of Orochi. Having been revived by Kiyomori Taira and Da Ji, this new form of Orochi is more powerful and evil than before. He utilizes his same scythe as his first form, but has a more powerful moveset.
Benkei was a warrior monk of the Heian period, most famously known for his loyalty to Minamoto no Yoshitsune, and his collection of weapons. He wields a giant glove (which conceals a cannon, flamethrower, a wooden block connected to a chain and a jet) as his weapon and is under the "PWR" category
San Zang is the central character of the classic Chinese epic Journey to the West, where Sun Wukong also originated from. However, in a break of traditional portrayals, Sanzang in Warriors Orochi Z is portrayed as a female. Her weapons are her sleeves, a la House of Flying Daggers and is under the "SPD" category
Dodomeki and Gyuki, two Orochi army generals that were only playable in the VS and Survival mode of Warriors Orochi 2, have been made into fully fledged characters that can be used throughout the entire game, complete with updated and improved movesets.