PSG has now secured the season-opening trophy on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the French league champions and the Coupe de France winners after the French winger found the net early on.
Yet, Marseille struck twice late to take a shock lead. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last 13 seasons.
