The Parisian club has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain needed 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 title.
The Champions League holders seemed to be sailing towards a straightforward win in the match featuring the French league winners and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial leveler in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the last thirteen seasons.
