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They've already enjoyed one successful collaboration when they joined forces for 2010 hit Love The Way You Lie.
And Rihanna and Eminem made sure to delight the A-list audience at the 2014 MTV Movie Awards at Los Angeles' Nokia Theatre on Sunday night when they performed their latest track, The Monster, live on television for the first time.
Headlining the two-hour show, the musical duo debuted their new offering with an energetic rendition ahead of their upcoming mini-tour which is set to travel to Los Angeles, New Jersey and Detroit this summer.
Scroll down for video and full list of winners
Talented twosome: Rihanna and Eminem made sure to delight the A-list audience at the 2014 MTV Movie Awards at Los Angeles' Nokia Theatre on Sunday night when they performed their latest track, The Monster, live on television for the first time
Introduced by Orlando Bloom, Rihanna entered the stage first, opening with stunning vocals as she as she bounded around the stage in an eye-wateringly tiny white minidress and a sporty padded baseball jacket.
The 26-year-old singer was joined by the rapper shortly afterwards, who mirrored her street style in a khaki baseball jacket, baggy charcoal jeans and a monochrome motif tee.
Performing alongside a full backing band, the pair managed to overcome technical faults to perform a crowd-pleasing rendition of their hit single for the first time on live television, which had the entire audience on their feet.
Monster performance: Headlining the two-hour show, the musical duo debuted their new offering with an energetic rendition ahead of their upcoming mini-tour which is set to travel to Los Angeles, New Jersey and Detroit this summer
Earlier in the evening, the Bajan beauty put on a typically daring sartorial display as she arrived on the red carpet, looking ready for bed in her sexy ensemble.
Sporting a long white satin robe over a plunging playsuit, Ri-Ri arrived with the slinky robe wrapped around herself but then cheekily opened it to reveal her ample cleavage for the bank of photographers.
The singer looked typically glamorous with her long black hair curled and tied up in a loose updo teamed with glossy lipstick and heavy black eye make-up, while strappy sandals and a chunky pendant necklace completed the look.
Star host: Orlando Bloom welcomed the pair onto the stage prior to their performance
Dream team: Rihanna and Eminem first collaborated on 2010 single Love The Way You Lie before reuniting for The Monster - which Eminem, 41, released as the fourth single from his album The Marshall Mathers LP 2
Cream of the crop: Rihanna entered the stage first, opening with stunning vocals as she as she bounded around the stage in an eye-wateringly tiny white minidress and a sporty padded baseball jacket
Rihanna and Eminem first collaborated on 2010 single Love The Way You Lie before reuniting for The Monster - which Eminem, 41, released as the fourth single from his album The Marshall Mathers LP 2 in October 2013.
Speaking previously about working with Rihanna, he said that The Monster was 'not necessarily a sequel, as much as it is a revisitation' to his past.
He added: 'To me, it's more about the vice, and it's more about the nostalgia.'
And the pair had no hesitations about joining forces once again for their new track.
Highlights from the MTV Movie Awards 2014
Musical maestro: The 26-year-old singer was joined by the rapper shortly afterwards, who mirrored her street style in a khaki baseball jacket, baggy charcoal jeans and a monochrome motif tee
Together again: Speaking previously about working with Rihanna, he said that The Monster was 'not necessarily a sequel, as much as it is a revisitation' to his past
Eminem told MTV News of their second collaboration: 'As soon as I got the beat, I just heard her on it. She smashed it, like she does always. It's pretty incredible.'
Meanwhile, Rihanna gushed: 'The moment I worked with him on Love The Way You Lie, I wanted to work with him again, and we did Love the Way You Lie (Part II).
'And then I wanted to work with him again. I just love working with Eminem.'
The thigh's the limit: The pair had no hesitations about joining forces once again for their new track
Ellie Goulding also took to the stage for a rendition of her single Beating Heart, which features on the soundtrack of recently released sci-fi action movie Divergent, while electronic DJ-producer Zedd, Matthew Koma and Miriam Bryant performed during the star-studded ceremony.
The Hunger Games: Catching Fire was the big winner of the evening, with leading lady and main man Jennifer Lawrence and Josh Hutcherson taking home Best Female and Best Male Perfomance respectively, while the sci-fi adventure scooped the coveted Best Movie prize.
Elsewhere, The Wolf of Wall Street and We're The Millers took home two awards apiece.
Ready for bed? Rihanna stepped out in a satin white robe and matching playsuit at the MTV Video Awards at the Nokia Theatre in Los Angeles on Sunday night
From demure to revealing: Rihanna arrived with her robe closed around herself before opening it to show off her toned figure
Centre of attention: Rihanna professionally posed for the slew of photographers outside the Nokia Theatre
MTV MOVIE AWARDS 2014 WINNERS LIST
BEST FEMALE PERFORMANCE
Jennifer Lawrence, The Hunger Games: Catching Fire
BEST MALE PERFORMANCE
Josh Hutcherson, The Hunger Games: Catching Fire
BEST MOVIE OF THE YEAR
The Hunger Games: Catching Fire
BEST ON-SCREEN TRANSFORMATION
Jared Leto, Dallas Buyers Club
BEST COMEDIC PERFORMANCE
Jonah Hill, The Wolf Of Wall Street
BEST VILLAIN
Mila Kunis, Oz The Great And Powerful
BEST SHIRTLESS PERFORMANCE
Zac Efron, That Awkward Moment
TRAILBLAZER AWARD
Channing Tatum
THE BEST KISS
Will Poulter Jennifer Aniston, and Emma Roberts, We're The Millers
BEST MUSICAL MOMENT
Backstreet Boys, Jay Baruchel, Seth Rogen and Craig Robinson perform in Heaven, This is the End
THE GENERATION AWARD
Mark Wahlberg
BREAKTHROUGH PERFORMANCE
Will Poulter, We're the Millers
BEST SCARED AS-S*** PERFORMANCE
Brad Pitt, World War Z
BEST ONSCREEN DUO
Vin Diesel and Paul Walker, Fast & Furious 6
BEST CAMEO PERFORMANCE
Rihanna, This Is The End
BEST HERO
Henry Cavill as Clark Kent, Man of Steel
#WTF MOMENT
Leonardo DiCaprio, The Wolf of Wall Street
FAVOURITE CHARACTER
Shailene Woodley, Divergent
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