Périer made his film debut in 1938 with appearances in La chaleur du sein and Hotel du Nord, the latter starring his mentor Jouvet. He earned his first male lead in the 1942 comedy Mariage d’amour. On stage, he made a strong impression as Hugo in Jean-Paul Sartre’s 1948 production Les Mains Sales, and later performed in Sartre’s The Condemned of Altona and The Devil and the Good Lord.
His film career peaked with roles in Jean Cocteau’s Orpheus 1950 as Heurtebise, René Clément’s Gervaise 1956 for which he won the BAFTA Award for Best Actor in a Leading Role, and Federico Fellini’s Nights of Cabiria 1957 as Oscar. In 1967, he starred as the Superintendent in Jean-Pierre Melville’s Le Samouraï, and in 1969 played the Public Prosecutor in Costa-Gavras’s Z. He also appeared in Claude Chabrol’s Just Before Nightfall 1971. In 1981, he portrayed composer Salieri opposite Roman Polanski’s Mozart in a Paris production of Amadeus directed by Polanski.
Beyond acting, Périer narrated the French-language version of Disney’s Fantasia and provided commentaries for classical recordings. Diagnosed with Alzheimer’s disease in 1991, he continued working in radio and film, with his last appearance in the 1996 crime drama Mémoires d’un jeune con.