The married couple will present a one-off episode on 23 August, with The Saturdays singer calling the opportunity "a dream come true".
Marvin and Rochelle took to Twitter to share their excitement with their 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.
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Marvin and Rochelle will replace regular hosts Eamonn Holmes and Ruth Langsford for the day, and follow in the footsteps of other celebrity guests such as Emma Bunton and Jamie Theakston who have presented one-off episodes on the show.
The announcement comes after recent speculation that Marvin and Rochelle will be "the next Richard and Judy," as the television world is said to need another husband and wife presenting duo.
"Marvin and Rochelle are seen as the perfect pairing," an insider told The Sun. "There's a hope they will be popular with viewers because of their obvious chemistry and ability to take the mickey out of each other."
The couple, who recently welcomed their baby daughter Alaia-Mai in May, have been focusing on family life but could be planning their next career move into television, especially as Marvin has revealed he has no plans to launch a solo career after JLS split later this year.