The Parisian club has now secured the season-opening trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net early on.
Yet, Marseille fired twice in the closing moments to take a shock advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last 13 seasons.