The band will be joined by this year's nominees Tom Odell and Kodaline at The Electric Ballroom in Camden on January 21.
Odell, who recently won this year's Brits Critics' Choice Award, said: "Really excited to be playing this show for MTV with Vaccines and Kodaline. Should be a great night."
Conor Maynard, last year's MTV Brand New winner, will headline a second gig the following day at The Forum, with support from MTV Brand New for 2013 nominees Gabrielle Aplin and Little Nikki.
Other nominees in the running for the prize include Angel Haze, Disclosure, Ebony Day, Haim, K Koke and Rascals.
Public voting is now open on the MTV Brand New for 2013 website and will stay open until January 31. The winner will be announced on February 1.
Watch Tom Odell's video for 'Another Love' below: