PSG has now claimed the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the showdown between the Ligue 1 winners and the French Cup holders after the French winger found the net early on.
However, the southern French side fired twice late to seize a surprise advantage. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
