The Parisian club has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the French Cup holders after the French winger opened the net early on.
However, the southern French side fired two times in the closing moments to seize a surprise advantage. Initially, 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 grabbed a crucial leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
