Laurence Llewellyn Bowen, Anthony Head and Coronation Street's Vicky Entwistle will also feature.
This Morning's Fern Britton and Phillip Schofield will present the show, which is based around couples correctly answering questions about each other.
"It's an iconic show that I watched as a child. I can't believe that I've been given this opportunity to revive it and I'm really looking forward to it," said Britton.
The couples will battle it out to win £30,000 for a charity of their choice.
All Star Mr & Mrs airs on ITV1 in the spring.