PSG has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the French Cup holders after the French winger found the scoring in the opening stages.
However, Marseille fired two times in the closing moments to take a surprise advantage. 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 remarkable turn of events, the Portuguese striker grabbed a vital leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time champions Paris Saint-Germain, 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 12th time in the last 13 seasons.
