The Parisian club has now won the season-opening cup on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown between the French league winners and the French Cup winners after the French winger opened the net early on.
However, Marseille fired two times late to seize a surprise lead. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital leveler in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
