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The singer will also perform a stripped-down version of her hit single 'Problem' during the show which is set to air from MTV's Times Square studio on Wednesday, July 2.
The second offering from Grande's upcoming sophomore album will arrive early next month.
Other performers at the event include Imagine Dragons, who performs their 'Demons' and 'Radioactive', and big winner Hedley who kicks off the show with 'Crazy for You'.
In addition to the Nickelodeon star and her collaborator, the Nev Todorovic-directed music video features an appearance from Big Sean who whispers the song's hook.
The Nickelodeon star performs the hit single alone as her collaborator Iggy Azalea, who previously performs 'Fancy' on the competition, has to leave first.
The Nickelodeon star says the song is special to her because it's one of the first songs she did when she started working on her first album, 'Yours Truly'.
The Ryan Seacrest-hosted concert also features performances by Ed Sheeran, Calvin Harris, Shakira, and Maroon 5.
In one of the photos shared on Instagram, the Nickelodeon star is seen donning a super mini outfit and a pair of white boots while sitting on a motorcycle.
The 'Problem' singer is seen smooching her former beau and showing off PDA backstage at Los Angeles' Shrine Auditorium.
After Bieber congratulates Grande on her chart-topping new single and posts a photo of them hanging out in a studio together, the Nickelodeon star says, 'Secrets out now.'
The hit single, which has topped iTunes charts since its release earlier this week, is predicted to make its debut in the top 10 on Billboard 100 next week.
The annual awards-giving show also features performances from other artists including Austin Mahone, Fifth Harmony and Zendaya Coleman.
The preview features Azalea rapping the verses she has recorded for the song that's scheduled to be debuted in full on April 27.
The singer takes to Instagram to preview 'a little part from the lyric video' because the music video hasn't been shot yet.
The Nickelodeon star will perform the new single when she takes the stage at Radio Disney Music Awards later this month.