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Castaño grew interested in acting. He also became a fan of soccer as a child.
Castaño's debut as an actor came in 1995, when he played Maria Jimena Piccolo's brother, "Christian", also known as "Mosca" in the Telefe telenovela, "Chiquititas", produced by Cris Morena. Castaño sang "El Beso" ("The Kiss"), a ballad, on Chiquititas' soundtrack. "Mosca" was a strong, healthy teenage boy who was suddenly diagnosed with muscular dystrophy. He went to Cuba to receive treatment and then returned to the orphanage where he and his sister "Jimena" lived at.
After "Chiquititas", Castaño acted in 1998's "Verano del '98", where he once again acted alongside fellow "Chiquititas" stars Agustina Cherri, Celeste Cid, Catalina Artusi, Diego Mesaglio and Guido Kaczka, among others. In "Verano del '98", Castaño played "Lucio Herrera".
Ezequiel Castaño then took four years off before returning to acting on the screen. When he returned, he participated in 2002's "Franco Buenaventura, el Profe" "(Professor Buenaventura)".
In 2010 Castaño played the role of Lalo Roldán, a football player, in the Argentine telenovela Botineras produced by Edemol and Underground, broadcast by Telefe. His character is having a same-sex relationship with his teammate Manuel (El Flaco) Riveiro.