PSG has now won the season-opening trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the French league champions and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side fired twice late to take a shock lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the past 13 seasons.
