The couple gracefully walked the blue carpet hand-in-hand at the private event, which was in support of Great Ormond Street Hospital, at Kensington Palace. In tow with the couple was their eldest son Maddox, 12, who looked all grown up in a leather jacket.
Jolie, who plays the titular villainess, looked gorgeous (as always) in a long sequined Atelier Versace black gown with an open back. The 38-year-old's engagement ring from fiance Pitt was on full display as she embraced the 12 Years a Slave actor to pose for pictures.
Pitt, 50, matched his love in an all-black ensemble and ombre-lensed glasses.
The Disney film, which opens in theaters on May 30, also features the couple's youngest daughter, 5-year-old Vivienne, who takes on the role of young Princess Aurora.
But not all of Jolie's kids were open to their mother being the Mistress of All Evil.
In an interview with Entertainment Weekly back in March, the Oscar winner revealed her costume even scared her 10-year-old son Pax.
"When Pax saw me for the first time, he ran away and got upset—and I thought he was kidding, so I was pretending to chase him until I actually found him crying," Jolie recalled. "I had to take off pieces [of the makeup] in front of him to show him it was all fake and not freak out so much."