The baking legend was all smiles as she posed for photos next to Nadiya, who won the most recent series of GBBO, and both looked simply stunning.
Mary wore a floor-length nude gown and she teamed it with a string of chunky pearls. Nadiya, meanwhile, opted for a black and gold dress with matching headscarf.
Great British Bake Off scooped the award for Best Feature and Mary and Nadiya collected the gong together. While on stage, Mary paid tribute to hosts Mel and Sue, who were not present at the event.
She said: "What a thrill. I'm not normally in charge up here but, tonight, Mel and Sue have landed me in it. I love them dearly and miss them, as we are a real team."
Handing the mic over, Nadiya added: "So I didn't prepare anything! Like Mel and Sue, Mary has landed me in it! It's an absolute honour to be on the show. It's incredible and one of the best things I've ever done. Long may it continue!"
The BAFTAs kicked off at London's Royal Festival Hall at 8pm this evening and the red carpet saw an array of famous faces.
Former TOWIE girls Ferne McCann and Lucy Mecklenburgh were spotted, along with Michelle Keegan and hubby Mark Wright.