The Parisian club has now claimed the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the match between the French league winners and the French Cup holders after the French winger opened the scoring early on.
Yet, the southern French side fired two times late to seize a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial leveler in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past 13 seasons.