PSG has now secured the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the showdown between the French league winners and the Coupe de France winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a surprise advantage. First, the English forward scored 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, the Portuguese striker snatched a crucial equaliser in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last 13 seasons.
