He has co-founded a Monaco-based team with Gildo Pallanca Pastor, owner of electric carmaker Venturi Automobiles.
Formula E racing starts next year, with the aim of giving a boost to the electric vehicle market, reported BBC online.
"The future of our planet depends on our ability to embrace fuel-efficient, clean-energy vehicles," DiCaprio said.
The 39-year-old actor's Venturi outfit is the 10th team to announce it is entering the series.
The racing series will compete in 10 of the world's leading cities including Beijing, Los Angeles, Miami, Buenos Aires, Berlin and London.
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