The 'Just Can't Get Enough' group will be joined by The Muppets star Kermit the Frog and the US first family at the Washington DC ceremony.
Ellie Goulding, Big Time Rush, One Republic and Rodney Atkins will also be in attendance at the tree lighting, which is to be hosted by The Voice's Carson Daly.
President Calvin Coolidge began the tradition of publicly lightning the White House's Christmas tree in 1923.
This year's tree is a Balsam fir, which has been shipped to Washington DC from Neshkoro, Wisconsin.
The National Christmas Tree lighting ceremony begins at 5pm local time on Thursday.
Last night, The Voice's Javier Colon, Justin Bieber and Neil Diamond all performed on Christmas in Rockefeller Centre in New York City.
> Justin Bieber unveils 'All I Want for Christmas is You' duet video
> Justin Bieber, Cee Lo Green join TNT's Christmas In Washington
Watch last year's National Christmas Tree lighting below: