Chris Martin, Guy Berryman, Jonny Bucland and Will Champion will perform Princess Of China with their fellow chart-topper at the O2 next February.
It will be the first time they have played the track, from Coldplay's hit album Mylo Xyloto, live together.
But it won't be the first time Rihanna has duetted at the show. She's been trying to erase the dodgy duet with Klaxons from her memory since the ceremony back in 2008.
The team behind the show have been working on the 2012 event for months and the line-up is taking shape fast ? Adele, Noel Gallagher and Kasabian have all got on board, too.
A Brits source said: "Coldplay are really looking forward to performing Princess Of China with Rihanna already. Brits bosses set their sights on getting them on stage together early doors. They are two of the biggest acts around right now."
Noel will play as a solo artist for the first time at the biggest night in British music after some memorable moments at the bash over the years.
Adele will be looking to kick-start her year after a recordbreaking 12 months by singing Someone Like You.
She is still recovering from throat surgery, but should be back to her best by then.
She could well sweep the board on the night, so expect some giggly acceptance speeches and a few tears.
This year's show was the best I can remember, with the format changing to include more live music than ever.
James Corden will return as host in 2012 after rave reviews for his second effort earlier this year.
Last night a spokesman for The Brits said: "We are still confirming the line-up, which will be announced with the nominations in January.
"We are working to make it the best show yet, with the biggest names in music performing."
All they need is a bit of Lady Gaga and some One Direction or Bieber for the kids and the job's a good 'un.