PSG has now secured the season-opening trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, Marseille struck two times late to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a convincing penalty victory.
Now 14-time 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 trophy for the 12th time in the last 13 years.
