PSG has now won the prestigious trophy on fourteen different occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice late to take a shock lead. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, 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 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last 13 years.
