Couve de Murville joined the corps of finance inspectors in 1930, and in 1940 became Director of External Finances of the Vichy régime, in which capacity he sat at the armistice council of Wiesbaden. In March 1943, after the American landing in North Africa, he was one of the few senior officials of Vichy to join the Free French. He left for Algiers, via Spain, where he joined General Henri Giraud. On 7 June 1943, he was named commissioner of finance of the French Committee of National Liberation (CFLN). A few months later, he joined General Charles de Gaulle. In February 1945, he became a member of the Provisional Government of the French Republic (GPRF) with the rank of ambassador attached to the Italian government.