The 'Titanic' star will work with staff at Christie's in New York for the 11th Hour Auction, which includes 33 works by the likes of Banksy, Peter Beard and Julian Schnabel, reported Daily Star.
The money raised by the sale will fund innovative conservation projects chosen by the Leonardo DiCaprio Foundation and an expert panel of environmentalists.
"My Foundation has worked on environmental issues since 1998, and despite the great efforts by organizations all over the world, our planet is in trouble.
"Given that less than 2 per cent of philanthropic giving goes to environmental conservation projects, we are grateful that Christie's and the participating artists are providing this incredible opportunity," he added.
The auction will take place at Christie's in New York on Monday.