PSG has now secured the season-opening cup on 14 separate occasions.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, Marseille fired two times late to take a shock lead. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who faced 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 seasons.