PSG has now claimed the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, the southern French side struck two times late to seize a shock lead. First, the English forward converted from the spot-kick, before the defender unfortunately 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 force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for PSG to complete a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 years.
