The premature boy and girl, both 5lbs and healthy, are Knox Leon and Vivienne Marcheline.
They were delivered by Caesarean in Nice, France, at 8pm on Saturday as dozens of security guards patrolled inside and outside the hospital.
Angelina had been due to give birth in August but it was brought forward for medical reasons.
Michel Sussmann, her doctor at the Lenval Hospital, said: “Mother and babies are doing very well. Everything is marvellous.”
Marcheline is named after Jolie’s actress mother who died of cancer last year.
Knox Leon is thought to be named after Brad’s grandad Hall Knox Hillhouse.
Leon comes from the Greek word for lion and implies strength.
Brad, 44 — who was present at the birth — and Angelina, 33, also have a daughter Shiloh, two, and three adopted kids.
The couple recently moved into a chateau 50 miles away and are due to be flown back there by helicopter later this week.
The babies’ first photo has been sold to a US paper for £5.5million with the money to go to a humanitarian cause.