The singer will play a set at Camden's Roundhouse in London on September 14 as part of the month-long series of free gigs.
"Playing live music is the thing I enjoy most, there's nothing like performing for the fans and getting that amazing energy back from them," Labrinth said.
"I had an amazing time performing for iTunes at Abbey Road, but I'm looking forward to being part of the festival as it's that chance to connect with people that I love."
One Direction, Rebecca Ferguson, Usher, Ed Sheeran, JLS and Jack White are among the other performers confirmed to play headline sets at the iTunes Festival 2012.
Watch the music video for Labrinth's 'Express Yourself' below: