The story follows the introduction of an American cartographer to the royal family of Siam in the 1970s.
- Chris Sanders as Stitch, the cartographer and protogonist of the film. He is a skilled martial artist and is very agile. His signature color is blue.
- Tara Strong as Angel, the beautiful princess of the Siam who is Stitch's love interest and girlfriend. Her color is white, because she wears a white elegant dress and a light blue ribbon with an sapphire. She likes to get along with Stitch because she thinks he is good-looking and gentle at heart. Considered a slight damsel-in-distress, she has been kidnapped by Leroy and his Dark Fire Warriors when the Empreor's guards have been knocked down during their fight but saved by Stitch.
- Sab Shimono as Master Ju-Yong, the student of Great Master Rai-Hun and the trainer of Stitch. His color is navy blue.
- Randall Duk Kim as Great Master Rai-Hun, the wise master of Sapphire Palace, and the senior trainer of Ju-Yong and Stitch. His color is blue-green.
- Soon-Tek Oh as the Empreor of Siam, Angel's father and friend of Great Master Rai-Hun. His color is green and orange.
- Miguel Ferrer as Leroy, the Dark Fire demonic sorceror who seeks to marry Angel. His signature color is red and black.
- Jim Cummings (uncredited) as Rem, the first Dark Fire Warrior, he is the red reptilian lizardman-like creature. He had a boomerang axe, similiar to Battle Axe (and materialized with a magma effect). His color is blue and violet.
- John DiMaggio (uncredited) as Han, the second Dark Fire Warrior, he is the green cyclopic humanoid. He had a sledgehammer (and materialized with a smoke-like affect). His color is black and brown.
- Maurice LaMarche (uncredited) as Jui, the third Dark Fire Warrior, he is the blue-and-violet humanoid wolf. He had a bo staff/Sa Tjat Koen (with a pouring-in effect). His color is black and purple.