Mum-of-one Rochelle, 25, joined her Saturdays bandmates on the show to perform their new single 'Not Giving Up' and promote their upcoming Greatest Hits Tour and album.
Rochelle may have been appearing on a daytime programme but she looked ready for a glitzy night out as she turned the London pavement into her catwalk in a flirty LBD that showed off her rather amazing legs.
The Saturdays have been on a promotional blitz over the past week, discussing everything from juggling babies with the band and whether their Greatest Hits announcement means they're splitting. (It doesn't).
During a chat on Sunday Brunch at the weekend, the group chatted about their tour, which kicks off in September, revealing it will feature lots of dancers, costume changes and special effects.
Of course, the three babies of the band will be going along with them, with Rochelle joking: "There will be a lot of suitcases this tour. A lot of stuff! We'll make it work though, we always do."
Rochelle gave birth to daughter Alaia-Mai in October 2013, while bandmate Frankie Sandford became a mum to son Parker in October 2013 and Una Healy has a daughter Aoife Belle, two.
"We're touring in September and only over the period of a couple of weeks so it won't be too challenging, really," predicted Una.
Frankie, meanwhile, joked: "I think management have released that maybe their childminding skills will come into it. Here you go, take the baby, see you later!"
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Watch The Saturdays' video for 'Not Giving Up' below: