PSG has now won the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, Marseille struck two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a convincing penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past 13 years.
