The 21 Jump Street actor joins three-time Oscar winner Meryl Streep for next month's charity show.
Elton John, James Taylor, Smash's Katharine McPhee and Rosanne Cash have previously been announced as the event's performers.
Sting – who runs the Rainforest Foundation with wife Trudie Styler – will also take part in the festivities on April 3.
Styler and Sting founded the charity organisation in 1989 to help preserve rainforests around the globe.
The 2012 Rainforest Foundation Benefit Concert is held on April 3 at Carnegie Hall in New York City,
Tickets are on sale now at the Rainforest Foundation's website.
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Watch Sting's 'Fortress Around Your Heart' music video below: