Angelina wowed in a floor-length cream satin gown with a side slit that cut up to her thigh.
The asymmetric dress by Atelier Versace had a red fold across the chest, which Angelina, 36, matched with a miniature clutch bag and some bright pillarbox lipstick.
Stealing the show: Angelina Jolie and Brad Pitt were the best-dressed couple on the Golden Globes red carpet
She also tied her brunette locks in an elegant bun and slipped some cream peep toe high heels onto her feet to complete the stunning look.
Brad, 48, wore a classic tuxedo by Tom Ford, with satin lapels and a bow tie to the star-studded event.
'It's a golden night for us,' he told E! host Ryan Seacrest, referring to the pair's double nomination.
Brad was up for Best Actor in a Drama and Best Motion Picture Drama for Moneyball, which he produced and starred in.
However, he lost out to his close friend George Clooney, who was joined at the event by his girlfriend Stacy Keibler.
George had introduced Brad's film Moneyball at the ceremony, while Brad returned the favour and introduce The Descendants.
Already winners: The stylish couple are rumoured to be presenting an award, and are also both nominated for Globes
Meanwhile Angelina's directorial debut, In the Land of Blood and Honey, was nominated in the Best Foreign Language Film category.
When asked about the film, she said: 'I was nervous about people in Bosnia seeing it who survived war and rape.'
'It's a very difficult subject matter, it's done in a foreign language, and with people nobody knows,'she explained.
Elegant: Angelina opted for a classic bun to complete her look
Angelina's film did not win, however, with that honour going to Iranian film A Separation.
She did make an appearance on stage though, presenting the Best Director for Motion Picture honour to Martin Scorsese for Hugo.
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