PSG has now secured the season-opening trophy on fourteen different times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
Yet, Marseille struck twice late to seize a surprise advantage. 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 twist of fortune, the Portuguese striker snatched a vital equaliser in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to seal a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last 13 seasons.