The supermodel duo will be joined by musician Noel Gallagher to take part in the one-off episode to support Cancer Research's Stand Up For Cancer campaign on 17 October.
"The sketch will help to raise money for charity and Kate is good friends with Noel and Naomi," a source told the Mail Online. "When she knew she would have them by her side she did not hesitate to agree."
Naomi Campbell supporting Kate Moss at the launch of her latest collection for Topshop
"Kate likes watching TV and is a fan of Gogglebox, Bake Off and X Factor," they added.
Gogglebox follows a series of different families across the UK, filming their reactions and critiques as they watch the week's biggest and best TV shows.
While Naomi, 44, is famously outspoken and known for her brutal honesty, Kate, 40, rarely publicly shares her opinions, so fans of the supermodel are excited to get an insight into some of her thoughts.
The pair have been friends for over 25 years and are often spotted together at events and parties, however this will make for a rare television appearance together.
Naomi has previously spoken about her relationship with Kate, explaining why their friendship is still going strong.
"She's honest, loyal and straightforward," she told the Evening Standard. "She's not pretentious in any way. What you see is what you get. I love that about her."