PSG has now won the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown featuring the French league winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
However, the southern French side struck twice in the closing moments to take a surprise lead. 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 grabbed a crucial leveler in the final moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty win.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.