PSG has now secured the prestigious trophy on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger found the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a surprise lead. Initially, the English forward scored from the penalty spot, before the defender unfortunately 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 final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
