PSG has now claimed the season-opening trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the Coupe de France winners after the French winger opened the net in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a crucial leveler in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
