PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring early on.
However, Marseille fired two times late to seize a surprise advantage. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial leveler in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
