The project - from JJ Abrams and Supernatural creator Eric Kripke - takes place in a world where all forms of energy have mysteriously ceased to exist.
Esposito will play Captain Neville, a tough but refined military man with a secret agenda, according to TVLine.
The actor is best known for playing drug lord Gustavo 'Gus' Fring on AMC's Breaking Bad and recently appeared on ABC's Once Upon a Time.
He will also appear in a forthcoming episode of NBC's Community, while his film credits include 1992's Malcolm X and 1994's The Usual Suspects.
Iron Man director Jon Favreau will helm the Revolution pilot, which was picked up by NBC earlier this month.
Being Human's Tracy Spiridakos, Struck By Lightning actor Graham Rogers and Terra Nova actress Anna Lise Phillips will also star.
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