PSG has now secured the prestigious trophy on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown featuring the French league winners and the Coupe de France holders after the French winger found the net early on.
However, Marseille struck twice late to seize a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial equaliser in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past thirteen years.
