PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the French league champions and the French Cup winners after the French winger found the scoring in the opening stages.
However, the southern French side struck twice late to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
