Adventurer Bear Grylls and Sir Tom Jones will join them in pre-recorded sketches to celebrate the crowning of the King and the Queen Consort.
New pictures of Charles and Camilla have also been released.
The photos were taken by Hugo Burnand, who was the official photographer at their wedding in 2005.
In one picture, the pair stand together as they pose in blue outfits, and then sit separately on blue and gold chairs in the other two.
The photos were taken last month in the Blue Drawing Room at Buckingham Palace.
The concert on Sunday, 7 May will take place in the grounds of Windsor Castle in front of a crowd of 20,000 members of the public - as well as being broadcast across BBC television and radio.
Other names will appear in pre-recorded sketches that are being billed as revealing little known facts about the monarch - including former Strictly Come Dancing professional Oti Mabuse.
Winnie the Pooh will make an appearance that could match that of the Platinum Party At The Palace in 2022, where the late Queen shared tea with Paddington Bear.
The latest names join a billing that already includes Take That, Katy Perry and Lionel Richie, as well as classical acts including Andrea Bocelli and Welsh bass-baritone Sir Bryn Terfel.
Music acts Paloma Faith, Olly Murs, veteran rock guitarist Steve Winwood, Nicole Scherzinger of The Pussycat Dolls and Chinese pianist Lang Lang have been added to the line-up too, along with Nigerian singer-songwriter Tiwa Savage, DJ Pete Tong with his Ibiza Classics project, and the teenage winner of The Piano TV talent show, Lucy.
Bollywood star Sonam Kapoor has also been chosen to deliver a spoken performance, which she said she would be "honoured" to do.
Kate Phillips, BBC director of unscripted, said: "Against the stunning backdrop of Windsor Castle, it's going to be a jam-packed evening of memorable moments, that Their Majesties and everyone in the UK can enjoy".
As well as the new photos of the King and Camilla, a previously unreleased picture taken of Charles while he was a student at Cambridge University has also been shared.
Charles was 18 when the picture was taken at his matriculation - which is when an undergraduate formally becomes a student at the university - in October 1967. It has been preserved in Trinity College's archives since then.
The King's Coronation will take place on Saturday 6 May at Westminster Abbey in London.
On Saturday, it was announced that the King would be anointed behind a private screen during his crowning.
The three-sided, embroidered screen will offer the monarch more seclusion than his predecessors enjoyed while the Archbishop of Canterbury uses holy oil to make the sign of the cross on the King's hand, breast and head.
About 150 people were involved in producing the embroidery, including some from the Royal School of Needlework, livery companies and fabric firms.