PSG has now won the season-opening trophy on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
