PSG has now won the prestigious trophy on 14 different occasions.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the French league winners and the French Cup winners after the French winger opened the scoring early on.
Yet, Marseille fired twice in the closing moments to seize a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a convincing shootout win.
Now 14-time winners 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 competition for the 12th time in the past 13 years.
