Joined by Bruno Mars, B.o.B and Williams performed a medley that also included "Nothin' on You" and Paramore's "Only Exception" at the 2010.
Beginning with this spring's anthem "Nothin' on You," Mars crooned his way through the track's chorus until an energetic B.o.B appeared on the other side of the Nokia Theatre stage. "Give it up to my homie, B.o.B," Mars screamed.
After bringing the song to a pause, B.o.B transitioned into his other 2010 smash, "Airplanes." Decked out in a white ensemble, Williams walked through a misty entrance as she met the MC at center stage.
"Can we pretend that airplanes/ In the night sky, are like shooting stars?/ I could really use a wish right now/ Wish right now, wish right now," she belted.
The duo sang smiling and dancing slightly side by side, as a lightning backdrop flickered in the background. With the song coming to an end, Williams walked to the back of the stage as "Only Exception" began to play. Joined by her band, the frontwoman grabbed a mic. As she sang the track, a sea of golden light bulbs were suspended above their heads.
During rehearsals for the big performance on Saturday, MTV News asked B.o.B what fans could expect from his and Hayley's VMA set. "I think just the fact that me and her are performing on the stage at the same [event] is gonna be spectacular," he told us.
B.o.B and Williams were nominated for Best Collaboration Video for "Airplanes," but lost out to Lady Gaga's "Telephone," featuring Beyoncé.
What did you think of B.o.B and Hayley's first-ever joint performance? Tell us in the comments!
The Moonmen have all been handed out and the stars have gone home, but there's plenty of 2010 MTV Video Music Awards news, interviews, behind-the-scenes scoop, party reports and more still to come, so keep it locked on MTVNews.com.