The Parisian club has now won the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a shock lead. Initially, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final moments 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, Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to seal a convincing shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen years.