The son of André Devambez, Pierre Devambez joined the École normale supérieure in 1922 and passed the agrégation es lettres in 1926.
A member of the French School at Athens (1928–1933) and of the Institut Français d'Archéologie Orientale, he sojourned in Istanbul from 1933 to 1937 and wrote there the Catalogue des Grands Bronzes.
Curator and chief curator of the Department of Greek and Roman antiquities at the Louvre from 1937, he was also in charge of Greek ceramics course at the École du Louvre.
Providing classes at the École Normale Supérieure (1954), he moved the classical archeology seminar in the halls of the Louvre.
A director of a seminary in Archaic and Classical Greek religion at the École pratique des hautes études (1961–1967), he was elected a member of the Académie des inscriptions et belles-lettres in 1970 and would preside the international commission of the Corpus vasorum antiquorum.