Rihanna, who is the youngest solo artist in US chart history to score 14 number one singles, will open the VMAs with a medley of some of her biggest hits.
The ceremony on Sunday US time will see Adele battle it out for the top awards with Beyonce, who has the most nominations with 11.
Adele, who has eight nominations, is up for video of the year for her smash-hit single Hello.
While Beyonce has been nominated in the same category for her Black Lives Matter-themed video Formation.
The women will compete against Drake's Hotline Bling, Justin Bieber's Sorry and West's controversial video Famous, which features nude waxworks of himself and a host of celebrities including his wife Kim Kardashian West, Donald Trump and Taylor Swift.
West, who famously interrupted Swift's acceptance speech at the 2009 VMAs, will attend this year's show and has reportedly been promised four minutes of stage time at the event.
He will be joined by his wife Kim, who is handing out an award.
Swift, who has no VMA nominations this year, is not expected to attend the ceremony.
Adele and Beyonce will compete with Rihanna, Sia and Ariana Grande for the best female video prize.
West and Drake are nominated in the best male video category, along with Bryson Tiller, Calvin Harris and The Weeknd.
The MTV VMAs take place at Madison Square Garden at 9pm on Sunday (1pm NZ time 29 August Monday).
