Initially a lukewarm member of the Polish Reformed Church, under the influence of Jesuits and his first wife he converted from Calvinism to Catholicism.

After careful studies at home and abroad (mostly in France and in the Netherlands) he began his great military career by fighting the rebels with his father and uncles on the side of King Sigismund III at the Battle of Guzów.

He took part in the war with Sweden (1626–1629) temporarily replacing Stanisław Koniecpolski, and suffered a major defeat at Górzno in 1629.

Potocki was also Starost of Halych, Radom, Krasnystaw, Ropczyce, Medyka, Bar, Grodziec, Kolomyia, Mostyska, Drahimów, Letychiv and Dolina.

In the 1656–1660 campaigns Potocki was not the supreme commander of the entire forces of the Crown, however he did have control over his division which took part in the battles.

In 1660, acting jointly with Jerzy Sebastian Lubomirski, Potocki was victorious over the Russian army led by Vasyl Sheriemietiev, forcing him to surrender at Cudnów.