PSG has now won the season-opening trophy on fourteen separate occasions.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup winners after the French winger found the net early on.
However, Marseille fired two times in the closing moments to take a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the last thirteen years.
