The band announced the news earlier today on Twitter, revealing that they'll be playing the Rio de Janeiro festival on September 14, 2013.
Metallica, Bruce Springsteen and Iron Maiden will also perform at next year's Rock in Rio.
Muse's appearance forms part of their 2013 tour of Europe and Japan, which includes a stadium tour of the UK in May.
Matt Bellamy said of the tour: "I think it's going to be our best tour so far. It's like our version of [Pink Floyd's] 'The Wall'. We've built this upside down pyramid structure which is full of video screens.
"Throughout the gig, it gradually comes down and consumes the band. So we end up eaten up by this pyramid thing, which is all very symbolic, of course. We blast out of it and escape.
"It's going to be a big experience. This is our Stonehenge tour!"
Muse recently cancelled three European concerts because singer Matt Bellamy has broken his right foot.
Watch Muse's video for 'Madness' below: