PSG has now claimed the season-opening trophy on 14 different occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after the French winger opened the scoring early on.
However, the southern French side fired two times late to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
