The Parisian club has now secured the season-opening cup on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward triumph in the match between the French league winners and the French Cup holders after the French winger found the scoring in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital equaliser in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
