The Parisian club has now won the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.
