The Parisian club has now claimed the prestigious cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net early on.
Yet, the southern French side struck twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately 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 dying seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen years.