The 45-year-old singer chose a plunging black gown that boasted a thigh-high split, echoing Angelina's iconic black velvet dress at the 2012 Oscars.
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Unlike Angelina's gown, Jennifer's dress has some gold and cut-out detail, however the striking similarities between the two looks are not surprising, as both designs were created by Atelier Versace.
Fashion's elite stepped out for the event, with supermodels Naomi Campbell and Karolina Kurkova gracing the red carpet in cream ensembles. While Naomi opted for a dress with silver detail, Karolina chose a demure crop top and pencil skirt combo, with her hair styled in old Hollywood glamour waves.
Model Joan Smalls also showed off her style credentials in a bright, patterned dress which showed off her stunning figure.
The 26-year-old, who recently revealed that she has collaborated on collection of lipsticks with Estée Lauder, opted for nude make up to contrast her colourful outfit.
Fashion Rocks, which celebrates fashion and music, also saw pop superstars Rita Ora and Nicki Minaj making waves on the red carpet with their stylish and sleek ensembles.
Rita, who performed onstage later in the evening, chose a one-of-a-kind black dress with a sheer back and detail, as well as a black train, while Nicki opted for a chic black playsuit teamed with bronze stiletto heels.