PSG has now secured the season-opening cup on fourteen different times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net in the opening stages.
Yet, the southern French side struck twice late to seize a surprise lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past thirteen years.
