The pair – who teamed up to perform a tap dance routine to Puttin’ On The Ritz – triumphed in a final which saw them compete against five other celebrity performers recreating classic routines.
Comedian Russell Kane, who dressed up as Beyonce to perform the routine to Crazy In Love, was runner-up.
The other participants in the final included Katie Price, performing to Queen’s I Want To Break Free and comedian Noel Fielding, who delivered his take on Kate Bush’s Wuthering Heights routine.
Ade Edmondson, performing the Dying Swan from Swan Lake, and an 80s supergroup consisting of Limahl, Chesney Hawkes Toyah and Clare Grogan dancing to Greased Lightning completed the line-up.
Afterwards the pair – who were visibly taken aback by their win – thanked everybody who had voted for them.
“Everyone who makes this show is amazing and everyone in this show has been great today. We’ve had an absolutely brilliant time and thank you very very much,” Charlie said.
“I want to say thanks to everyone who voted at home. We’ve raised so much money for a brilliant cause and that’s what it’s all about. We’ve had a real laugh while we’ve been doing it, cheers guys!” added James.
Earlier in the show Charlie and James had won praise from the judges for the reprisal of their routine, which featured some complex tap dancing moves.
“Charlie I have known you for a long time and I didn’t expect you ever to be doing that,” said comedian Rufus Hound, who won last year’s Let’s Dance For Sport Relief and joined the judging panel for the final. “I haven’t enough so much clip clopping since I moved underneath that bridge. Well done!”
And Louie Spence, who was also on the panel, said of the pair, “They were not tap syncing, they were knocking out clean beats.
“You had great fluidity through the moves as well. It was beautiful and your rhythms were great, so well done and would be more than happy to be your Ginger Rogers!”
The previous Let’s Dance For Comic Relief in 2009 was won by comedian Robert Webb with his recreation of the title song from Flashdance. Rufus Hound’s take on Cheryl Cole‘s Fight For This Love won 2010’s Let’s Dance For Sport Relief.
Proceeds from the show’s phone votes will go to Comic Relief, with this year’s Red Nose Day telethon set to take place on Friday March 18.