The Blurred Lines beauty, 27, dressed to impress in a see-through dress, while chart-topper Rita, also 27, wowed in a colourful gown that flashed some serious leg.
The Anywhere hitmaker might have been left regretting her choice of her frock when it came to posing on the red carpet however.
While smiling for snaps Rita could be seen incessantly adjusting the design at the waist to ensure the breezy weather didn't have her flashing more than she bargained for.
Once inside, Rita performed for the exclusive guestlist in a typically eccentric white costume that featured large feathered sleeves and a glitzy, see-through fabric.
"Tonight was so inspiring being able to perform for a charity that I will continue to work so closely with on helping children in need," she wrote on Instagram after her emotive show.
"It’s so important to use your platform for good and motivate others to do the same! Thank you @unicef for having me as one of your ambassadors along side some incredible individuals. Lots of love Forever, yours truly, R."
Nicole Scherzinger also wowed in a red silk crop top that showed off her toned tum and a floor-length skirt with sexy criss-cross detailing.
Ahead of the event Nicole, who is in a relationship with tennis star Grigor Dimitrov, shared an inspirational message with fans.
"Let your hopes, not your hurts, shape your future. Never lose #Hope. You never know what tomorrow will bring," she enthused.
Model Heidi Klum, 45, set pulses racing in a plunging black dress as she walked the red carpet arm-in-arm with new toy boy Tom Kaulitz, 28.
The couple began dating in March, shortly after Heidi's split from art curator Vito Schnabel, 32,who has since moved on with actress Amber Heard.
Victoria's Secret beauty Jasmin Tookes, Ricky Martin and Shanina Shayk were also on the exclusive guestlist.
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