While Brangelina were both a model of sophistication during their television interviews, Jolie cheekily let her guard slip towards the end of her marathon media stint on the red carpet.
When asked what she was most looking forward to from the evening, AP reports she winked and whispered: "Getting into bed with Brad."
Jolie's quip was one of several priceless celebrity moments from the Beverly Hilton Hotel that television viewers never got to see.
The star-studded bash, hosted by the Hollywood Foreign Press Association, has a reputation for being more light-hearted and relaxed than the Academy Awards, and plenty of stars were happy to let their hair down.
[ Related: Pitt and Jolie visit the White House ]
Mark Wahlberg was in such fine spirits while chatting to friends at the outer bar that he had to be hurriedly ushered backstage to present the award for best actor in a comedy to Jean Dujardin.
Moments earlier Wahlberg, whose love of boxing increased while making "The Fighter," had been discussing his wish for fight superstars Manny Pacquiao and Floyd Mayweather to finally meet in the ring.
While much discussion focused on the dresses of the leading ladies, there was little doubt as to the identity of the most expensively-clad star. Sofia Vergara was wearing an estimated $5 million-worth of glittering jewelry from Harry Winston and confided in a friend that the responsibility of taking care of the extraordinary ensemble left her feeling like she was "going to have a heart attack."
[ Photos: Red carpet report card ]
Many celebrities found that their commitments on the red carpet meant they were too late to be served the lavish meal concocted by chefs Suki Sugiura and Thomas Henzi, which featured a chocolate dessert that included edible gold flakes.
During an early commercial break, friends Salma Hayek and Nicole Kidman were heard gushing over each other's dresses. Meanwhile Queen Latifah arrived fashionably late, apologizing profusely, after being overwhelmed by pre-ceremony interview requests.
A trip to the men's restroom provided more than one unexpected dose of entertainment. Jonah Hill appeared bewildered when an attendant offered him an eye roller — a free gift offered by L'Oreal and designed to reduce wrinkles under the eyes — and refused to try it out.
The simmering feud between Sir Elton John and Madonna showed no sign of abating, with hostilities beginning more than an hour prior to the ceremony. Elton snappily told a reporter that Madonna had "no (expletive) chance" of winning Best Original Song, while Madonna later retorted by asking if her rival "was wearing a dress."
[ Video: Madonna talks Lady Gaga ]
"May the best man win," Madonna added — and she would have the last laugh, scooping the Globe for "Masterpiece," featured in the movie "W.E."
While some stars were happy to lap up the attention, others preferred to do things their own way. Charlize Theron showed little love to the red carpet photographers, scooting past the waiting line at the post-show In Style and Warner Bros. party instead of posing on the red carpet.
Then there was show host Ricky Gervais, who was asked if he was okay by a concerned attendant after swearing loudly backstage. "Absolutely," Gervais beamed. "I do this when I'm happy."
Fortunately, given his presenting responsibilities, Gervais remained until the end, which was more than can be said for Nicole Kidman and Keith Urban, who slipped out a few minutes before the final award for Best Motion Picture was given to "The Descendants."
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