PSG has now secured the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net early on.
Yet, Marseille fired two times late to take a surprise lead. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past 13 seasons.
