According to The Sun, Daniels and his wife Debbie McGee will play suspects in a case about a missing golf trophy.
The BBC show's stars Philip Glenister, Keeley Hawes and Dean Andrews will interrogate the pair.
"Philip and Keeley were only too happy to take part for Sports Relief. The support from the cast and guest stars was overwhelming," said a source.
"It was a very cold day but everyone pulled together. It's going to be a real highlight of the money-raising effort and Gene's got some great put-downs for Paul."
Spandau Ballet's Tony Hadley, Michael Parkinson, ex-footballer Peter Shilton, snooker star Willie Thorne and golfer Sam Torrance also cameo in the short film.
The Ashes To Ashes special will air on March 19.