PSG has now won the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck twice late to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from 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 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the last thirteen seasons.
