The 68-year-old star was the special guest at the first of the 24-year-old singer-songwriter's three sold out London gigs and the pair performed two songs together, Elton's 'Don't Go Breaking My Heart' and Ed's 'Afire Love'.
The 'Thinking Out Loud' hitmaker was clearly in the mood to celebrate as he's the first solo artist to ever headline the huge venue without the help of a backing band.
Ed previously revealed he was planning to get a tattoo to mark the incredible achievement.
He said: ''Originally I was going to get the floor plan tattooed on my side, but that seemed a bit ridiculous.''
He eventually decided to opt for a lion as it's the England soccer team's home stadium and that is their logo.
Ed added: ''It's going to hurt.''
Another reason to celebrate was the fact his album 'x' has returned to the number one spot in the UK album charts more than a year after its initial release.
In addition to his duets with Sir Elton, Sheeran kept the 90,000 strong crowd singing along with renditions of his hit singles 'Lego House', 'A Team' and 'Sing'.
Check out Ed's journey - from selling CDs out of his backpack in tiny pubs in London to sold out shows at Wembley Stadium - here: http://roadtowembley.edsheeran.com/
Ed's set list in full was as follows:
'I'm a Mess'
'Take it Back'/'Superstition'
'I See Fire'
'Don't Go Breaking My Heart'
'Give Me Love'
'I Was Made To Love Her'
'Thinking Out Loud'
'You Need Me'
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