Martín was particularly noted for his work in the Spaghetti Western genre, alongside regulars such as Aldo Sambrell and Andrea Scotti, with supporting roles in Savage Guns (1961), Gunfighters of Casa Grande (1964), Minnesota Clay(1964), A Pistol for Ringo (1965), Seven Dollars on the Red (1966), Arizona Colt (1966), A Bullet for the General (1966), Blood River (1967), 100 Rifles (1969), and Cut-Throats Nine (1972).

He also had memorable roles in EuroHorror films such as Sax Rohmer's The Castle of Fu Manchu (1969), The Sinister Eyes of Dr. Orloff (1973), Count Dracula's Great Love (1974), and Curse of the Devil (1974).

He initially studied at the Teatro Español Universitario in Madrid with José Luis López Vázquez, María Jesús Valdés and Valeriano Andrés before obtaining a scholarship at the Lope de Rueda.

This was followed by minor roles in Ángel Vilches' adventure film A dos grados del ecuador (1953), the Luis Lucia comedy Aeropuerto (1953), and Rafael Gil's religious-themed historical dramas I Was a Parish Priest (1953) and Judas' Kiss (1954).

He received his first supporting role, as Muñoz, in Gil's next film Murió hace quince años (1954) appearing alongside Rafael Rivelles, Francisco Rabal and Lyla Rocco.

Martín's prolific appearances made him was one of the most recognizable Spanish actors involved in the genre, rivaling those of fellow Spaghetti Western regulars such as Aldo Sambrell and Andrea Scotti, and is considered one of the best villains of the era.

In the late-1960s and 70s, Martín starred in Spanish horror films such as Sax Rohmer's The Castle of Fu Manchu (1969), The Sinister Eyes of Dr. Orloff (1973), Count Dracula's Great Love (1974), and Curse of the Devil (1974).