PSG has now won the season-opening trophy on fourteen separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the Coupe de France winners after the French winger opened the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned 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. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time winners 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 12th time in the past 13 years.
