Befitting her dark, magical character, she chose a dramatic strapless black leather gown created by Versace, that featured a sweeping train.
Angelina, 38, was supported on her big night by her brood – with the exception of little Vivienne, who appears alongside her mum in the Disney film.
Brad Pitt and Angelina Jolie held hands on the special blue carpet
She was joined by her proud fiancé Brad Pitt and five of their six children; Maddox, 12, Pax, ten, Zahara, nine, Shiloh, eight, and Vivenne’s five-year-old twin Knox.
The couple looked absolutely smitten as they cuddled up on the premiere's special blue carpet, Brad frequently stopping to whisper sweetly in Angelina’s ear.
Brad and his boys wore suits for the premiere – as did Shiloh, who Angelina has previously said "thinks she is one of her brothers".
Zahara, meanwhile, embraced the magical spirit of the film by getting stars painted on her arms and face.
Angelina Jolie greets some children dressed as mini Maleficents
Sadly, the family’s night out was tainted. Brad, 50, was struck in the face by a Ukrainian serial prankster while on the red carpet.
Vitalli Sediuk jumped over the barrier and hit the actor before security quickly intervened and he was arrested.
Brad carried on greeting fans and a police spokesman confirmed he was not seriously hurt. Angelina was in another section at the time signing autographs.
It’s not the first time Vitalli Sediuk has struck; just last week he tried to put his head under America Ferrera’s skirt in Cannes, and in 2012, Will Smith angrily slapped him in the face when he tried to kiss him at the Men in Black 3 premiere.