The stunning star wowed on the red carpet with her elegantly structured Atelier Versace dress, which showed off her curves to perfection. The gown was split to Angelina's thigh, and was ruched at the waist to accentuate her petite curves.
The actress teamed the frock with a red clutch bag to match the sweeping neckline. Angelina also opted to wear the crimson shade on her famously pouty lips.
She kept her hair simple and swept off her face in a low bun.
A host of other Hollywood faces stunned on the prestigious event's red carpet. White shades seemed to take centre stage, with Charlize Theron wowing in a daring Dior gown. The gorgeous actress showed off her décolletage with a plunging neckline, and ensured her perfectly toned legs were also on show.
The gown's hem was higher at the front, and gathered into a sweeping train at the back.
Stunning redheads Jessica Chastain and Nicole Kidman also wowed in neutral shades. Nicole looked edgy yet elegant in a studded cream dress by Versace. Jessica looked a picture in a white, high collared, Givenchy gown with Harry Winston pearls.
Meanwhile, Jessica Alba and Kate Beckinsale chose a romantic pink shade to wow at the glitzy Hollywood event. Jessica opted for a sparkly Gucci gown for her red carpet moment, while Kate looked gorgeous in a simple strapless Roberto Cavalli creation.
Claire Danes and Kate Winslet wowed in monochrome. Kate chose a simple Jenny Packham floor length number, while Claire opted for an embellished backless gown by J Mendel.
The actress accessorised with Bulgari jewels.
Sofia Vergara looked stunning in a figure-hugging Vera Wang dress which showcased her famous curves. The dark blue fishtail gown set-off her olive complexion to perfection.
Sofia teamed the look with Harry Winston diamond earrings and cuffs.
Many stars opted for classic black on the red carpet, including Rooney Mara, Julianna Moore and Mila Kunis.
The black-and-white silent film The Artist came away with the most prizes with three wins, but the show spread the love around among a broad range of films and TV shows.
Ricky Gervais, who has ruffled feathers at past shows with sharp wisecracks aimed at Hollywood's elite and the Globes show itself, returned as host for the third-straight year.
Wins for The Artist included best musical or comedy and best actor in a musical or comedy for Jean Dujardin, while the family drama The Descendants claimed two awards, as best drama and dramatic actor for George Clooney.
Other acting winners were Meryl Streep, Michelle Williams, Christopher Plummer, and Octavia Spencer, while Martin Scorsese earned the directing honour.
Streep won for dramatic actress as Margaret Thatcher in The Iron Lady, her eighth win at the Globes.
Williams won for actress in a musical or comedy as Marilyn Monroe in My Week with Marilyn, 52 years after Monroe's win for the same prize at the Globes.
Dujardin won for musical or comedy actor for the silent film The Artist.
The supporting-acting Globes went to Plummer as an elderly widower who comes out as gay in the father-son drama Beginners and Spencer as a brassy housekeeper joining other black maids to share stories about life with their white employers in the 1960s Deep South tale The Help.
Scorsese won for the Paris adventure Hugo. It was the third directing Globe in the last 10 years for Scorsese, who previously won for Gangs of New York and The Departed and received the show's Cecil B. DeMille Award for lifetime achievement two years ago.
He won over a field of contenders that included Michel Hazanavicius, who had been considered by many in Hollywood as a favourite for his black-and-white silent film The Artist.
Williams offered thanks for giving her the same award Monroe once won and joked that her young daughter put up with bedtime stories for six months spoken in Monroe's voice.
"I consider myself a mother first and an actress second, so the person I most want to thank is my daughter, my little girl, whose bravery and exuberance is the example I take with me in my work and my life," Williams said.
Dujardin became the first star in a silent film to earn a major Hollywood prize since the early days of film.
He won as a silent-era star whose career unravels amid the rise of talking pictures in the late 1920s.
It is a breakout role in Hollywood for Dujardin, a star back home in France but little known to US audiences previously.
His French credits include The Artist creator Michel Hazanavicius' spy spoofs OSS 117: Cairo, Nest of Spies and OSS 117: Lost in Rio.
The Artist, which led the Globes with six nominations, also won the musical-score prize for composer Ludovic Bource but lost out on three other awards, including the screenplay prize for Michel Hazanavicius.
Woody Allen won the screenplay honour for his romantic fantasy Midnight in Paris, the filmmaker's biggest hit in decades.
Never a fan of movie awards, Allen was a no-show at the Globes, where he previously won the screenplay honour for 1985's The Purple Rose of Cairo.
The wins boost Williams, Spencer and Plummer's prospects for slots at next month's Academy Awards, whose nominations come out January 24.
The Oscars are an honour for which Monroe herself never was nominated, though she was a two-time nominee at the Globes and won for best actress in a musical or comedy for 1959's Some Like It Hot.
In My Week with Marilyn, Williams plays Monroe as an insecure performer struggling to establish herself as a genuine actress rather than a movie star sexpot just a couple of years before Some Like It Hot.
The film chronicles Monroe's contentious time shooting the 1957 romance The Prince and the Showgirl alongside exasperated director and co-star Laurence Olivier.
Like Monroe, Oscar consideration has been elusive for the 82-year-old Plummer, who has been nominated for Hollywood's top honour only once in his 60-year career - two years ago, for the Leo Tolstoy drama The Last Station.
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