The 'Fireworks' singer, 28, wore a stunning leopard-print dress embellished with gold dragonflies, which was only matched by her bold accessory - her bejewelled teeth grill.
Like Madonna and Rihanna before her, Katy showed off the latest bling accessory taking the States by storm.
Forcing her to sneer rather than smile, though, Katy eventually took the dental diamonds off to be able to beam properly at the cameras.
Her dress, complete with thigh-high slit, clung to every curve of her famous body - and was one of the best seen on the red carpet last night (Aug 25).
She performed her first live performance of new single 'Roar', which she sang under the Brooklyn Bridge.
She closed the show with the first single from her upcoming album Prism in a spectacle that saw her performing in a full-sized boxing ring.
Lady Gaga opened the awards with the debut performance of her own new single 'Applause'.
Full List of 2013 MTV Video Music Awards winners below:
Video Of The Year: Justin Timberlake, 'Mirrors'
Best Hip-Hop Video: Macklemore & Ryan Lewis feat. Ray Dalton, 'Cant' Hold Us'
Best Male Video: Bruno Mars, 'Locked Out of Heaven'
Best Female Video: Taylor Swift, 'I Knew You Were Trouble'
Best Pop Video: Selena Gomez, 'Come and Get It'
Artist To Watch Presented by Taco Bell®: Austin Mahone, 'What About Love'
Best Collaboration: Pink feat. Nate Ruess, 'Just Give Me A Reason'
Best Video With A Social Message: Macklemore & Ryan Lewis, 'Same Love'
Best Rock Video: Thirty Seconds To Mars, 'Up In The Air'
Best Art Direction: Janelle Monae feat. Erykah Badu, 'Q.U.E.E.N.'
Best Choreography: Bruno Mars, 'Treasure'
Best Cinematography: Macklemore & Ryan Lewis feat. Ray Dalton, 'Cant' Hold Us'
Best Direction: Justin Timberlake feat. Jay-Z, 'Suit & Tie'
Best Editing: Justin Timberlake, 'Mirrors'
Best Visual Effects: Capital Cities, 'Safe and Sound'
Song Of The Summer: One Direction, 'Best Song Ever'
Michael Jackson Video Vanguard Award: Justin Timberlake
What do you think of the new craze for bejewelled teeth? Tell us your thoughts in the comment box...
Watch the lyric video to Katy Perry's new single 'Roar' below: