The '80s singer will be up against Britney Spears, Christina Aguilera, Green Day, Tokio Hotel and U2 in the category.
An internet craze named 'Rickrolling' saw Astley's hit 'Never Gonna Give You Up' register more than 13 million YouTube views earlier this year. The phenomenon saw fans posting a link to the track disguised as something else on their websites.
Madonna, Snoop Dogg, Weezer, Santogold and 30 Seconds To Mars are up for the video star award, MTV has also announced.
The awards will take place at the Liverpool Echo Arena on November 6, with Beyoncé confirmed to perform.