The troupe will be giving a rendition for their new single, React, as they have recently done on shows such as The One Show and Ant and Dec's Saturday Night Takeaway.
The fundraising programme is set to start at 7pm on Friday and will be hosted by Gary Lineker, Paddy McGuinness, Alex Scott, Oti Mabuse, Emma Willis, Tom Allen, Maya Jama and Rylan Clark-Neal.
It will also feature musical performances from KSI, Celeste and John Newman as well as world exclusive performance from Rita Ora of new track How To Be Lonely, which was written by Lewis Capaldi.
Pussycat Dolls Nicole Scherzinger, Ashely Roberts, Kimberly Wyatt, Jessica Sutta and Carmit Bachar have generated complaints to broadcasting watchdog Ofcom of late over their raunchy performances.
Their skimpy outfits and steamy routines in their pre-watershed slot have attracted criticism from some viewers.
She said: “Those costumes, we put that together in three days and those outfits were a bit provocative,” said the 41-year-old star.
“But we're women now.”
Scherzinger went on: “It takes courage to be that vulnerable.”
Meanwhile, Wyatt has insisted that the group is out to spread a "positive message" and that she's happy to let her daughters, who are five and two, to watch them perform.
She said: “They love it, they love seeing it and I love bringing them to dress rehearsals and things.
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“And teaching them what it means to be a Pussycat Doll and own your space as a female.
“I think it's a really positive message and it’s important for my girls to see that and understand what that means.”