The Parisian club has now claimed the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league winners and the French Cup winners after the French winger found the net early on.
Yet, the southern French side struck twice in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last thirteen seasons.
