Last night's premiere episode saw six celebrity acts competing in the first of three heats, hoping to impress viewers and the panel of judges.
Webb sailed through to the final round, receiving the highest number of public votes after performing a Flashdance routine.
Commenting on the result, he told viewers: "Thank you very much. I did wish to entertain the ladies and gentlemen. I feel all shy now!"
Dick and Dom and EastEnders stars John Partridge and Cliff Parisi, who were runners-up in the vote, then found their fates depending on the panel of judges.
After Michael McIntyre voted in favour of the soap actors and Emma Bunton picked the presenters, head panellist Anton Du Beke had the deciding vote and chose to back Dick and Dom.
As well as Partridge and Parisi, Les Dennis, dance partners Christopher Biggins and Nicki Chapman and the Chefs - including John Burton Race and Paul Rankin - were eliminated.
Let's Dance For Comic Relief continues next Saturday on BBC One. The final takes place on March 14.