PSG has now secured the prestigious trophy on fourteen separate times.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the match featuring the French league champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired two times in the closing moments to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.