PSG has now won the season-opening trophy on 14 separate 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 fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the match between the French league winners and the Coupe de France holders after the French winger opened the net early on.
However, Marseille struck twice late to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to seal a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last 13 years.
