The pop couple presented a one-off episode on 23 August, with The Saturdays singer looking natural and relaxed in her TV role, as she worked alongside her husband.
The new mum wore a floral Dolce & Gabbana dress very similar to the one she wore to the One Direction premiere on Tuesday evening, with black high heels and her hair in loose curls. Marvin, meanwhile, looked dapper in a burgundy suit with a black shirt and shoes.
Fellow The Saturdays singer Frankie Sandford took to Twitter to share her delight and support at seeing the duo on the popular morning show.
"Argh! Look who it is!! Naturals! @rochellethesats", wrote the pregnant singer.
Una Healy saw from the Twittersphere that her bandmate was doing 'great'. She wrote: "From your tweets sounds like our @RochelleTheSats and Marvin are doing great on This Morning."
Leigh from girl group Little Mix revealed herself as a new fan of the couple, posting, "Aww I'm loving @rochellethesats @marvinhumes on @thismorningitv they're such a cute couple! :) x leigh".
Marvin and Rochelle replaced regular hosts Eamonn Holmes and Ruth Langsford for the day.
Although the pair looked completely relaxed, it looks like Rochelle hid her nerves well. Just hours before she was live on the silver screen, she tweeted, "Can't sleep I am so excited to be hosting @itvthismorning with my hubby @MarvinHumes tune with us at 10.30am on ITV eekkkk!"
Upon confirming their foray into presenting at the beginning of the month, Rochelle called it "a dream come true".
She quickly shared her excitement with fans. "The rumours are true for those of you who are asking! @MarvinHumes and I will be hosting @itvthismorning on Aug 23rd we're very excited ! Xx," tweeted Rochelle, in a post that was mirrored by her husband.
"It's a dream come true that we're now going to be hosting This Morning, we can't wait for our first show," she added.
The couple follow in the footsteps of other celebrity guests such as Emma Bunton and Jamie Theakston who have presented one-off episodes on the show.