The Parisian club has now secured the prestigious cup on fourteen different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a straightforward triumph in the match featuring the French league champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, the southern French side struck twice late to seize a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
