PSG has now secured the prestigious trophy on 14 different occasions.
Paris Saint-Germain required a dramatic leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring early on.
However, Marseille fired twice in the closing moments to seize a shock lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.