Ed Sheeran was joined by Elton John as they performed one of his greatest hits Don't Go Breaking My Heart, originally recorded by John and Kiki Dee in 1976.
Singer Ella Henderson shared a video of the performance on Twitter and thanked the Thinking Out Loud singer for an "insane night", and for "the pleasant surprise" of John's appearance, reported Digital Spy.
Watch the performance here
The pair followed up their performance of John's classic hit with a rendition of Sheeran's Afire Love, taken from his album X.
The shows at Wembley mark the first time a solo act has headlined the venue without the backing of a band and last night was the first of three sold-out gigs for the singer.