A wider audience became aware of Smits for his appearance as Senator Bail Organa of Alderaan who becomes Princess Leia's adoptive father, in the Star Wars film Episode III: Revenge of the Sith. He also appeared in the Star Wars film, Episode II: Attack of the Clones.

He also starred in the multigenerational story of a Chicano family in My Family/Mi Familia in 1995. Smits also played the Conky Repairman on Pee-wee's Playhouse as one of the show's memorable characters, and in one of his earliest roles. Another notable early role played by Smits was that of Eddie Rivera in the series premiere of Miami Vice. In the episode, he was Sonny Crockett's original partner, only to be shortly killed off in a sting gone wrong.

Smits played the role of Congressman Matt Santos of Houston, Texas in the final two seasons of the American television drama The West Wing, joining fellow L.A. Law alumnus John Spencer. The series ended with Santos' inauguration as President of the United States after winning the presidential election. He defeated moderate Republican Senator Arnold Vinick of California (played by Alan Alda). The producers of the series reported that they had not decided early on who would win, and in fact reported to The New York Times that until Spencer's death, they had planned on electing Vinick. (wikipedia.org)