He was the Elector of King Władysław IV representing the Bratslav province in 1632. He was also the Elector of King John II Casimir in 1648 from the province of Podolia. During the Khmelnytsky Uprising, it is believed that Potocki saved the king's life near the town of Zborów. In 1652 he was appointed the Field Hetman of the Commonwealth and two years later he commanded the Polish army against the Russians and Cossacks. In 1655 he fought and won the Battle of Ochmatów. In the same year he was nominated the voivode of Kiev. After the invasion of the Swedish army during the Deluge he was permanently commanding the army in the East, however not engaging against the Swedes. After the defeat of the Russian-Cossack army under Gródek Jagielloński Potocki was forced to surrender to King Charles X Gustav. He later joined the confederation at Tyszowce. 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. He was one of the Hetmans that participated in the Battle of Warsaw in 1656. In 1657 he fought victoriously with George II Rákóczi, and took part in the pinning of his troops near Czarny Ostrów. 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. The last time he fought was against the Lubomirski rebels, suffering a defeat at Częstochowa in 1665. During his entire military career, he participated in 46 battles.