The singer replaces Keith Urban, who has moved over to American Idol.
Martin joins last year's coaches Delta Goodrem, Seal and Joel Madden for the show on the Nine network.
"Ricky Martin is one of the world's biggest stars," said Nine's director of television Michael Healy.
"He brings huge experience to our panel of coaches, which he'll pass on to our Australian Voice artists in 2013. Most of all, we think he's the perfect addition."
Kylie Minogue last month ruled out joining the 2013 panel, but added that she is "a fan of those shows" and that it "may only be a matter of time" before she signs up for one.
Watch the video for Ricky Martin's 'The Best Thing About Me Is You' below: