In 1978, Molina starred with Leonard Rossiter in the sitcom The Losers. Molina made his film debut with a minor role in the 1981 movie Raiders of the Lost Ark as Indiana Jones' ill-fated guide during its iconic opening sequence. However, his big break came with Letter to Brezhnev in 1985, which he followed up with a starring role in Prick Up Your Ears in 1987, playing Joe Orton's lover Kenneth Halliwell. He was given a lead role in the Red Dwarf TV series, but was replaced by another actor.
He starred in the first two series of El C.I.D. but left to concentrate on his film work. Subsequent films included Species, Dudley Do-Right, Chocolat, Not Without My Daughter, and Enchanted April. He has worked twice with Paul Thomas Anderson, first in Boogie Nights and then Magnolia. In 2002, Molina gained wide recognition for his portrayal of Mexican muralist Diego Rivera alongside Salma Hayek in the biopic Frida, a role which garnered him BAFTA and SAG award nominations. In 2003, he play