PSG has now claimed the season-opening cup on fourteen separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward win in the match between the French league winners and the Coupe de France holders after the French winger found the net in the opening stages.
Yet, the southern French side struck two times in the closing moments to seize a surprise lead. 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 remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 years.