The Parisian club has now claimed the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the French league winners and the French Cup winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired twice late to take a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the last 13 years.
