His repertoire included works by Jean Genet, Eugène Ionesco, Hugo Claus, Robert Musil, Anna Langfus and Anton Chekhov.

In 1967, he achieved his greatest success with a well-regarded production of Luigi Pirandello's Henry IV, which he directed and starred in, with Claude Jade.

He was featured in roles of various sizes in such films as Henri-Georges Clouzot's Les Espions (1957), Peter Ustinov's Lady L (1965), René Clément's Is Paris Burning?

He also appeared in several Hollywood productions, including Anatole Litvak's Anastasia (1956) and The Night of the Generals (1967), Mark Robson's The Prize (1963) and Dick Clement's To Catch a Spy (1971).

For the last ten years of his life, Pitoëff was a professor at the National School of Theatre Arts and Techniques (ENSATT) in Lyon, where his students included Gérard Depardieu, Jean-Roger Milo and Niels Arestrup.