The British musician is among the acts singing Elvis tracks for the show, which will air on February 17, on what would have been the rock icon's 84th birthday.
Bosses at U.S. network NBC also announced that Post Malone, Alessia Cara, John Legend, Shawn Mendes, Adam Lambert, Blake Shelton, Jennifer Lopez, Carrie Underwood, Keith Urban, and Kelsea Ballerini will perform during their "Elvis All-Star Tribute" concert.
Ed will give his take on ballad "Can't Help Falling in Love", while other highlights include Jennifer's version of "Heartbreak Hotel", John singing "A Little Less Conversation", and Post and Keith teaming up for "Baby What You Want Me to Do".
Adam, who will sing "Blue Suede Shoes", told Variety: "Elvis defined pop culture in the '50s with his voice, style and swagger. He was one of the first icons I ever listened to, so to take the stage during this anniversary tribute feels like a big honour."
Taped in October, the tribute show will be hosted by Blake, with the King of Rock and Roll's widow Priscilla Presley and daughter Lisa Marie Presley also appearing.
The set for the programme pays homage to Elvis' famed 68 Comeback Special, which aired on NBC five decades ago, as the boxing ring-style stage from the original TV gig has been recreated.
Officially known as "Singer Presents...Elvis", it aired in December 1968, and was watched by 42 per cent of U.S. TV viewers. The performance helped re-establish the Hound Dog hitmaker as one of America's biggest stars after a commercial lull following several years spent focusing on his film career.