Both will celebrate the launch of MTV's unsigned competition - a nationwide search to find one undiscovered act to join the Brand New 2013 shortlist announced in November.
"It's great to have MTV with me on my journey and it's a privilege to be asked to come back as an established artist," Labrinth said.
"I'm really looking forward to it. See you there!"
Ware added: "'I'm really looking forward to playing at MTV Brand New as I have watched MTV since I was a kid so to now be on it is wicked."
The event will take place at Armani's flagship store in London's Bond Street, following MTV's partnership with Emporio Armani Diamonds for the project.
Unsigned artists from around the UK are eligible to enter the competition between September 6 and September 28 at www.mtv.co.uk/brandnew. Entrants will then be put to a public vote in October, with the complete Brand New shortlist announced on November 28.
Last year's winner was Conor Maynard, who has so far gone on to score two top five singles and a number one album.
Watch the music video for Labrinth's latest single 'Treatment' below: