The Parisian club has now won the prestigious trophy on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup holders after the French winger opened the net in the opening stages.
However, Marseille struck two times late to take a shock advantage. First, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past 13 seasons.