PSG has now won the season-opening trophy on fourteen separate times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the match between the French league winners and the Coupe de France holders after the French winger opened the scoring early on.
However, Marseille fired twice in the closing moments to take a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to seal a 4-1 shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the last 13 seasons.
