Born at Pont a Mousson (Meurthe et Moselle, France). The son of an officer, he was educated at the military schools of his native town and of Châlons. He was gazetted second lieutenant, (artillery) in the 4th regiment in 1793, and advanced steadily in the service. Captain Duroc became aide-de-camp to Napoleon in 1796, and distinguished himself at Isonzo, Brenta and Gradisca in the Italian campaigns of 1796-1797.
He served in Egypt, and was seriously wounded at Aboukir. His devotion to Napoleon was rewarded by complete confidence. He became first aide-de-camp (1798), general of brigade (1800), and governor of the Tuileries. After the battle of Marengo he was sent on missions to Vienna, St Petersburg, Stockholm and Copenhagen.
As grand marshal of the Tuileries he was responsible for the measures taken to secure Napoleon's personal safety whether in France or on his campaigns, and he directed the minutest details of the imperial household. After Austerlitz, where he commanded the grenadiers in the absence of General Oudinot, he was employed in a series of important negotiations with Frederick William III of Prussia, with the elector of Saxony (December 1806), in the incorporation of certain states in the Confederation of the Rhine, and in the conclusion of the armistice of Znaim (July 1808).
In 1808 he was created duke of Friuli, and after the Russian campaign he became senator (1813). He was in attendance on Napoleon at the battle of Bautzen (May 20-21, 1813) in Saxony, when he was mortally wounded, and died in a farmhouse near the battlefield on May 23. Napoleon bought the farm and erected a monument to his memory.
Duroc was buried in the Invalides.