They will be joined by Calvin Harris, Paloma Faith and Clean Bandit at the inaugural ceremony at London's Earl's Court on Thursday, December 11.
BBC Radio 1's Nick Grimshaw and Radio 2's Chris Evans teamed up to make the special announcement.
Coldplay's Chris Martin said, "We're really looking forward to the BBC Music Awards. It's an incredible line-up and we're honoured to be part of it."
Meanwhile, Evans added, "Every year is a marvellous year for music in the UK and 2014 has been no exception. The inaugural BBC Music Awards will be the new icing on an ever mouthwatering end-of-term cake.
"We shall gratefully be tipping our hats to those whose lights have shone brightest and whose music has helped water the inner flowers of our souls, hearts and minds over the last 12 months.
"Call it a review with prizes, or a show full of surprises, I cannot wait. Get your ears on, the BBC Music Awards is coming to get you." Three awards will be presented at the ceremony, including British Artist of the Year, International Artist of the Year and Song of the Year. The latter will be decided by a public vote.
The BBC has promised that the night will feature surprise collaborations, as well as recreations of the best music moments of the year.