PSG has now claimed the prestigious trophy on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the French league champions and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck two times in the closing moments to take a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed 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 dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
