PSG has now secured the prestigious cup on fourteen different occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck two times in the closing moments to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the 12th time in the past thirteen seasons.