The Parisian club has now won the prestigious trophy on fourteen different occasions.
The Parisian giants required a dramatic leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille fired two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 seasons.