PSG has now won the season-opening cup on 14 different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the French league champions and the Coupe de France winners after the French winger opened the net early on.
However, Marseille fired twice late to take a surprise advantage. First, the English forward scored 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 leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last thirteen seasons.
