The Hollywood beauty is to play Disney villainess Maleficent.
Angelina is seen with the famous horned headpiece as she takes the title role of the Sleeping Beauty sorceress in the forthcoming fairytale spin-off, which has started production.
The 36-year-old - who is executive producer on the project - also has yellow eyes and chiselled cheekbones as she transforms from being doting mother-of-six and fiancée to Brad Pitt, into the self-proclaimed 'mistress of all evil' for the movie.
"I'm having a lot of fun. I've already got my horns fitted. My kids are very happy," she told Entertainment Weekly.
Elle Fanning, Sharlto Copley and Sam Riley are on board Robert Stromberg's directorial debut, alongside Imelda Staunton, Miranda Richardson, Juno Temple and Lesley Manville.
The 3D film, which has been written by Linda Woolverton and is scheduled for release in 2014, reveals the events that hardened Maleficent's heart and drove her to curse the baby, Aurora, played by Elle.
The 36-year-old also confessed it's good to be bad - although there are some redeeming qualities to the character.
"It sounds really crazy to say that there will be something that's good for young girls in this, because it sounds like you're saying they should be a villain," she said.
"It's not anti-princess, but it's the first time they're looking at this epic woman [in a different way]. It's a really great script."