PSG has now claimed the season-opening cup on fourteen separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele found the net early on.
However, Marseille fired twice late to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial equaliser in the final moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past 13 years.
