The pop star couple - who became first-time parents to daughter Alaia-Mai in May - were up bright and early and dressed to impress to host a one-off episode of the popular morning show.
Rochelle, 24, donned a pretty floral frock, which was cinched in at the waist with a thin belt to show off her slim post-pregnancy figure. Her long brown locks also looked enviably glossy and full of volume.
Meanwhile, 28-year-old Marvin opted for a purple coloured suit and a smart black shirt, which he teamed with a very special pair of shoes.
"I wore these shoes on my wedding day", he revealed. Aww!
One item of clothing that the JLS singer didn't have on however, was a low cut, V-neck T-shirt - something that he and his bandmates used to be famous for frequently wearing!
And apparently, his slight change in style is down to wife Rochelle.
During a rather heated debate about whether women should try to change their partners, the Saturdays songstress said that she had managed to alter a tiny aspect of her hubby's wardrobe and convinced him to ditch the V-necks.
"He had this thing of having a bigger cleavage than me… It was all a little bit too much for me!" she explained.
The loved-up couple also had a go at making some apple turnovers on the show with a previous star of The Great British Bake Off and Marvin attempted to use the opportunity to show off his (limited) kitchen skills.
But Rochelle was quick to put him in his place! "Marvin always says 'my dad's a chef so I can cook'", she said. "Don't encourage him."
Marvin then tried to explain why he hasn't bothered to learn how to bake, adding: "Rochelle is so good at cooking that I don't need to cook".
They certainly sound like a proper married couple!
Also on This Morning, the two pop stars treated two viewers to a stylish makeover and had a chat with Celebrity Big Brother presenter Emma Willis, who reassured them that they were doing a great job.
While on the sofa, Emma discussed another show that she presents - Girlfriends - and the trio then touched on the subject of dating.
"Dating was the worst time of my life," Rochelle announced to a surprised Marvin.
Well, she doesn't have to worry about that anymore!
Overall, we think the twosome did a fab job at presenting This Morning and, at one point, 'Marvin and Rochelle' even became a Twitter trending topic, so the fans clearly agree.
We'd love to see them back on our TV screens again soon.
Did you watch Marvin and Rochelle on This Morning? Let us know what you thought below, as the best comment each week wis £50!