He played the role of Eddie Carbone in A View from the Bridge several times, including Sidney Lumet's 1962 film adaptation, for which he won the David di Donatello for Best Actor.

He attended Liceo classico Cavour and studied law and philosophy at the University of Turin, where his professors included Leone Ginzburg and future President Luigi Einaudi.

[1] Vallone played association football from a young age, as a member of the Unione Libera Italiana del Calcio (ULIC) youth club for Turin, winning the championship for the 1930–31 season.

He played rugged, romantic leading men in the 1950s, including in Anna (1951) and The Beach (1954), both directed by Alberto Lattuada; Pietro Germi's The Crossroads (1951), and Giuseppe De Santis' Rome 11:00 (1952).

He was the male lead in Vittorio De Sica's Two Women, which earned its star Sophia Loren the Academy Award for Best Actress.

He played opposite Maria Schell in two West German films, Love (1956) and Rose Bernd (1957), and was cast by French director Marcel Carné in Thérèse Raquin (1953).

He subsequently starred in Jules Dassin's Phaedra (1962), Otto Preminger's The Cardinal (1963) and Rosebud (1975), Gordon Douglas' Harlow (1965), Henry Hathaway's Nevada Smith (1966), Peter Collinson's The Italian Job (1969), John Huston's The Kremlin Letter (1970), Lamont Johnson's A Gunfight (1971), Charles Jarrott's The Other Side of Midnight (1977), J. Lee Thompson's The Greek Tycoon (1978), Michael Ritchie's An Almost Perfect Affair (1979) and Moustapha Akkad's Lion of the Desert (1980).

He had a late-career boost when Francis Ford Coppola cast him as Cardinal Lamberto, the future Pope John Paul I, in The Godfather Part III (1990).