The 47-year-old actor and TV presenter - who announced in January she had ended her seven year relationship with Eddie Boxshall - has found a replacement for the city stockbroker on her sofa for the Channel 4 show.
James, 44, revealed on his Intagram stories: "Can't wait to start filming @c4gogglebox with my bestie @vanouten_denise."
Van Outen shared the post with a heart emoji.
The former EastEnders star - who is currently guest hosting Steph's Packed Lunch on Channel 4 - recently said she is "proud" of herself for knowing "when to walk away" from her former fiance, as he admitted to being unfaithful.
Van Outen told The Zoe Ball Breakfast Show on BBC Radio 2: “The one thing I’m really proud of myself for is I do know when to walk away and I don’t like to be taken advantage of.
"Sometimes it’s been to the detriment of my own career or in my own relationships, but I just feel like it’s really important as a woman to have self-worth and self-respect."
Boxshall has said he is "deeply sorry" for the sex texts he sent to another woman behind her back, which ended their relationship.
He told The Sun: "I hurt Denise, I broke her trust and I’m deeply sorry...I deeply regret that I sent those messages."
The TV presenter is mother to 11-year-old daughter Betsy, whose father is West End star Lee Mead.
Van Outen announced that she and Eddie Boxshall were no longer a couple in an Instagram post, saying she, "had to make the difficult decision not to continue in our relationship".
The couple met when one of Van Outen's friends set them up on a blind date.
Blue singer James, 44, is in a relationship with 28-year-old Rodrigo Reis.
The new series of Celebrity Gogglebox - which shows celebrities watching and commenting on the week in TV - begins in June.
Watch: Denise Van Outen reveals burglary at her home