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 secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup winners after the French winger found the net early on.
However, the southern French side fired twice late to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
