PSG has now secured the prestigious cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the match featuring the French league champions and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
