Robbie Williams' anticipated reunion with the Take That boys might have been the most talked about in the build-up to the event, but it was by no means the only exciting partnership on the night.
Part of the entertainment meant many of the acts performed duets with others from the concert.
This led to a few surprises, including a union between the nation's sweetheart Cheryl Cole and rock band Snow Patrol.
The X Factor beauty gave an impressive and energetic performance of her number one single Fight For This Love – similar to the one she performed on the talent show – before transforming into a long white gown to join the quintet.
She sang lines from their song Set Fire To The Third Bar, originally featuring Martha Wainwright.
Snow Patrol's Gary Lightbody admitted some people were surprised the band were performing with the pop star, but said there were definite perks to the job.
"Everyone gets a partner, it was like getting partner at school," explained the front man. "We got the prettiest girl in the class."
Perhaps the evening's most unusual pairing featured Dame Shirley Bassey.
After starring alongside Gary Barlow for a number, the Welsh artist gave a rendition of Diamonds Are Forever for which she was joined by Dizzee Rascal rapping alongside.
Annie Lennox, Lily Allen, Mika, Leona Lewis and Muse were also at the charity concert, held in the Royal Albert Hall.
The grand finale of the extravaganza was led by Beatles legend Sir Paul McCartney, who was joined onstage by all the evening's acts for a performance of Hey Jude.
Highlights for the gig will be shown on November 20 on Children In Need.