The X Factor girl group will perform their first single proper - 'Wings' - on the Simon Cowell game show, while contestants will be asked a crucial question centred around their routine.
Meanwhile, Dancing with the Stars professionals Derek Hough and Peta Murgatroyd will perform the Argentine Tango for another competition.
Hough's appearance is significant given his close friendship with Cheryl Cole, who famously fell out with Cowell after he axed her from The X Factor USA last year.
Other famous faces taking part in games during the episode include Premier League footballers Bobby Zamora and Darren Bent, who will race to knock out seven targets suspended on a swinging pendulum.
Red or Black?, again hosted by Ant and Dec, will launch its second series on Saturday (August 18) with Carol Vorderman, Jonathan Ross and Cover Drive as special guests.
The show, which has been given a revamp and format change following its controversial and much-criticised first series, will air after The X Factor at 9.15pm on ITV1.