The Parisian club has now won the season-opening trophy on fourteen different times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the match between the French league champions and the French Cup holders after the French winger found the scoring in the opening stages.
However, Marseille fired twice in the closing moments to seize a surprise lead. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last 13 years.
