The 51-year-old de Villepin replaces the unpopular Jean-Pierre Raffarin, who resigned after voters rejected the proposed European Union constitution Sunday by a 55 percent majority.
Previously, as foreign minister, De Villepin was a strong opponent of the U.S.-led war on Iraq, particularly in the United Nations. In Washington, the State Department said it did not object to the appointment.
"We look forward to working with the prime minister and his government when it's named," spokesman Richard Boucher said.
Chirac had promised cabinet changes in the event of a no vote.
Raffarin's economic reforms and poor record on jobs were widely blamed for the scale of Sunday's referendum defeat.
Replacing de Villepin at the Interior Ministry will be Nicolas Sarkozy, who has been heading Chirac's governing center-right party, which had campaigned for the Yes vote.