Ed was booked up for four dates at London's O2 Arena where he belted out his old and current hits with a stripped back performance of just his voice and his guitar.
Ed's concerts have received rave reviews and it seems Pulp Fiction star Samuel, who took a selfie with thousands of fans in the arena, was clearly blown away too.
"Caught @edsheeran last night," Samuel tweeted. "A mic, a guitar, A-mazing!"
It seems all the main action happened off-stage though, as Ed and Samuel went on a rather crazy selfie spree, which they've now both shared with fans on Twitter and Instagram!
The pair pulled a series of funny faces as they posed backstage. Referring to Samuel's Star Wars character, Ed said: "Chilling with Mace Windu."
Samuel even praised the singer-songwriter again, telling fans that Ed was the "real deal".
Taylor Swift, Jennifer Aniston and Harry Styles are just a few of Ed's BFFs, and we're guessing we can add Samuel to this list now!
Other stars spotted at Ed's London concerts over the past few days have been former TOWIE star Joey Essex and One Direction singer Niall Horan.
Ed, who has had a remarkable year with his chart-topping album X, is on tour throughout the UK until the end of this month.
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Watch Ed's video for 'Thinking Out Loud' below: