PSG has now won the prestigious cup on fourteen different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring early on.
However, the southern French side struck twice late to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the final moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty victory.
The record champions 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 13 seasons.
