PSG has now won the prestigious cup on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring early on.
Yet, the southern French side struck twice in the closing moments to take a surprise lead. 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 events, Goncalo Ramos snatched a crucial equaliser in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past thirteen seasons.
