Laid down in 1958, the ship was launched in 1962, and commissioned in 1964.
The ship was assigned to the 2° Gruppo Navale d’Altura (2nd High Seas Naval Group) of the II Divisione Navale (2nd Naval Division), based in Taranto. In the 1980s she was transferred to La Spezia, while her twin, the Andrea Doria, moved from there to Taranto.
The Caio Duilio then served as a school ship for the Accademia Navale di Livorno. It was decommissioned in 1990.