The Parisian club has now won the prestigious trophy on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net in the opening stages.
However, the southern French side struck twice in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 shootout 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 won this trophy for the twelfth time in the past 13 years.
