PSG has now secured the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to take a shock lead. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for PSG to complete a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen seasons.
