Fresh from their stint in the jungle, Kian and Rebecca will be hoping to win gold in the hotseat for their chosen charities.
Joining the all-star line-up is football manager Sir Alex Ferguson, who will be teaming up with daytime TV host Eamonn Holmes. The duo are hoping to beat their previous win of £32,000.
Eamonn said: "It will be a chance to see if Sir Alex still possesses his winning ways and if we can get the better of Chris Tarrant with our mind games. Although it's a tremendous honour to be invited back, the pressure is on to see if we can better our winnings."
Also hoping to win big is actress Caroline Quentin, who will be pairing up with Countdown legend and Loose Woman panellist, Carol Vorderman.
The six famous faces will join quiz master, Chris Tarrant, for one of his last ever shows.
Chris will be overseeing proceedings and ensuring that participants are put to the test, and while the celebrities play for their favourite charities, a lucky viewer at home will also have the chance to split the cash.
This will be the last ever live show of Who Wants To Be A Millionaire, but several pre-recorded celebrity specials will air in early 2014.
Tune into Who Wants To Be A Millionaire? on Thursday 19 December at 9pm on ITV.