PSG has now claimed the season-opening trophy on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the net early on.
However, the southern French side fired twice late to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing shootout victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen years.
