The Parisian club has now won the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, Marseille fired twice late to take a surprise lead. Initially, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
