The couple, who have four children and two more on the way, signed a three-year lease on the 880-acre estate called Chateau Miraval, where neighbors will include Johnny Depp and David and Victoria Beckham, according to the French newspaper Nice Matin.
The estate, reportedly valued at $70 million, comes with its own vineyard, olive groves, lake, moat, 20 fountains and even a forest to help ensure privacy.
"They'll have total privacy, which is exactly what they're after," a source told E! Online. "No one will ever be able to get pictures of them relaxing at home, it's just impossible."
At the Cannes International Film Festival, Jolie, 32, who is expecting twins this summer, told reporters that she was thinking of giving birth in France, and that French is the "second language" in the family's home.
A rep for Pitt and Jolie had no comment on the estate.