Music
Rex Features
The duo will collaborate at the event, which takes place at Liverpool Echo Arena on November 6.
Previously announced performers at the awards show include Take That, Beyoncé, Pink, Duffy, The Killers and Kid Rock.
"With Estelle and Kanye West joining the lineup in Liverpool, MTV can definitely claim credit for the broadest range of artists for any live show this year," said the show's executive producer Richard Godfrey.
"With both artists performing for the first time at the Awards, this is a real coup for MTV's global audience."
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