The Parisian club has now claimed the season-opening trophy on 14 different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward triumph in the match featuring the French league champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck twice in the closing moments to seize a shock advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a vital leveler in the final moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 years.
