PSG has now won the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille fired twice late to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 years.
