Last year's runners-up will perform new single 'Everybody In Love', released on the following day.
Bon Jovi will play their single 'We Weren't Born to Follow' ahead of the launch of their new album The Circle, also out on November 2.
Last week's live performances from Whitney Houston and Cheryl Cole drew an audience of 13.17 million.
JLS release their self-titled debut album on November 9.
> Click here to watch our recent video interview with JLS