The 35-year-old singer will perform for the Ball's 1,500 guests after the Oscars on March 2, 2014.
The guests will include Oscar winners, nominees, show presenters, performers, and other luminaries, according to a release by the Academy.
"John Legend is one of the industry's most innovative and talented artists. We're thrilled he will be joining us to celebrate this year's achievements in film, and for what promises to be a most memorable evening," said Jeffrey Kurland, Costume Design Branch governor and chair of the Governors Ball.
Legend's songs have also been included in the soundtracks of such films as 'Waiting for Superman', 'Think Like a Man' and 'Django Unchained'.
Academy Awards will be presented on March 2, 2014.