PSG has now won the season-opening trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the match featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille fired two times late to take a surprise advantage. Initially, 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 events, the Portuguese striker snatched a crucial equaliser in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a convincing penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.
