Stepping Out will see six celebrities team up with their real-life partners to master a different genre of dance for each week's show.
Former Westlife star Brian McFadden and wife Vogue Williams will compete in the programme, alongside Loose Women's Denise Welch and her husband Lincoln Townley - who she married in Portugal last month.
EastEnders actress Glynis Barber and her husband Michael Brandon, boxer Carl Froch and his girlfriend Rachael Cordingley, and interior designer Laurence Llewelyn-Bowen and his wife Jackie will also take part.
JLS singer Oritsé Williams and his girlfriend A.J Azari complete the celebrity lineup.
McCall - who also fronts Sky1's Got to Dance - said of her new hosting role: "I'm beyond excited to be hosting Stepping Out, I love dancing and I'm a nosey parker. I can't wait to see how the couples are going to cope trying to learn the cha cha or pirouette whilst doing the school run or cleaning."
ITV's Entertainment Commissioning Editor Kate Maddigan said: "We're really pleased to have Davina on board as host joining our lively mixture of couples.
"Davina's enthusiasm and energy will be a great asset for Stepping Out and perfect for bringing out the best in our celebrities and their real life partners."
Stepping Out is coming soon to ITV.