At Marengo on 25 Prairial in the year VIII (14 June 1800), he was made adjutant to Joachim Murat, commander of the cavalry.
Promoted to Brigadier General on September 4, 1802, he succeeded his brother Victor Léopold Berthier [fr] the following year as chief of staff in Paris, the latter being called to leave for Germany.
When he became "commander of Corfu," Caesar Berthier settled in the Fortezza Vecchia, in the building occupied before him by Venetian provveditores, general Antoine Gentili and Louis François Jean Chabot, then before that Sebastiano Mocenigo.
Although Napoleon promised that the Seven Islands would retain their independence, Berthier hoisted the French flag over the citadel, which was not seen as an encouraging sign by the local population.
Also in Italy he was appointed head of the house of Pope Pius VII, who was being held prisoner in Savona by Napoleon (1809-1814).