Willoughby, who first worked with Mulhern 20 years ago, has been off air since she left This Morning in October following 14 years on the sofa.
The pair appeared on Saturday morning children’s show Ministry Of Mayhem, later renamed Holly & Stephen’s Saturday Showdown.
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June: ITV bosses questioned over Schofield
Katie Rawcliffe, head of entertainment commissioning at ITV, said: “Holly and Stephen are two of our best loved presenters, so reuniting them 20 years after they first appeared on screen together to host Dancing On Ice marks the start of an exciting year for the show.”
Mulhern briefly joined Willoughby on the programme in 2022, stepping in after Schofield tested positive for COVID-19.
Judges Jayne Torvill and Christopher Dean, Ashley Banjo and Oti Mabuse will also return when the show begins in January.
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Former world champion boxer Ricky Hatton, Coronation Street actress Claire Sweeney, singer Hannah Spearritt, West End star Amber Davies and Olympian Greg Rutherford are among the stars taking part.
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TV personality Miles Nazaire, comedian and writer Lou Sanders, actor Ricky Norwood, radio presenter Adele Roberts, actor Ryan Thomas and Emmerdale’s Roxy Shahidi will also compete.
Former Gogglebox star Stephen Lustig-Webb was due to feature but was forced to pull out after breaking his left ankle during ice skating training, with Olympian Eddie “The Eagle” Edwards taking his place.