The Parisian club has now won the prestigious cup on fourteen separate occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the scoring early on.
However, the southern French side struck twice in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 seasons.
