Luis Santamarina rode the team time trial for Spain at the 1964 Tokyo Olympics, helping the team to an eighth-place finish. Santamarina turned professional shortly after Tokyo, riding for the Olsa team in 1965. He rode for Fagor from 1966-69 and was with Werner in 1970-72 before ending his pro career. Santamarina won the 1967 Spanish road title, but his biggest win came at the 1970 Vuelta Ciclista al Pais Vasco (Tour of the Basque Country). He also won the Vuelta a Aragon in 1970. He won two stages at the Vuelta a España, one in 1968 and one in 1970, and won a stage at the Giro d’Italia in 1968. Santamarina rode the Tour de France four times, with a best GC finish of 24th in 1971. He placed third at the 1967 Tour de Suisse, and ninth on GC at the 1970 Vuelta a España.