Belonging to a noble family, he entered the French Royal Navy and received rapid promotion, being named post captain in 1793 and rear admiral in 1796. He commanded a section of the French fleet in Napoleon's expedition to Egypt. His flagship, the Guillaume Tell, along with the Généreux, were the only warships to escape the French fleet's general destruction during the ensuing Battle of the Nile (Aug. 1, 1798).
Villeneuve played a key role in the failed execution of Napoleon's scheme for the invasion of England in 1805. In the autumn of 1804 Napoleon had named Villeneuve commander of the fleet at Toulon. The duty of Villeneuve's fleet was to draw the British admiral Horatio Nelson's fleet to the West Indies, return rapidly in secret, and, in combination with other French and Spanish ships, enter the English Channel with an overwhelming naval force for the invasion of England. Villeneuve apparently had little confidence in the success of this operation, but nevertheless he took the command in November. In March 1805 he sailed out of Toulon and succeeded in drawing Nelson after him in a cruise out to the West Indies. Villeneuve's fleet then returned to Europe in June-July, during which time it fought an indecisive encounter off El Ferrol, Spain, with an English squadron led by Sir Robert Calder.
Villeneuve then turned south to the port of Cádiz, disregarding Napoleon's standing orders to proceed immediately to the Channel and rendezvous with the other French and Spanish naval forces gathered there. This act of timidity on Villeneuve's part effectively ended Napoleon's hopes for an invasion of England while Nelson's fleet was somewhere else. In Cádiz Villeneuve then received orders to sail his fleet into the Mediterranean for an attack upon Naples, but, while making his preparations, he learned that another officer had been sent to replace him in his command. In a spasm of wounded vanity, he embarked his fleet out of Cádiz to face the waiting fleet of Nelson, and the result was the (q.v.) of October 1805. Villeneuve's impulsive decision to leave Cádiz and give battle to Nelson's better-prepared fleet has been severely criticized.
At Trafalgar Villeneuve showed personal courage, but the incapacity of the Franco-Spanish fleet to maneuver gave him no opportunity to influence the course of the battle, which ended for the French in complete defeat. Villeneuve himself was captured and was taken as a prisoner to England, but he was soon released. Shortly after returning to France he committed suicide at an inn in Rennes, where he had been waiting to learn the extent of the emperor's displeasure with him.