PSG has now won the prestigious cup on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring early on.
However, Marseille fired two times in the closing moments to take a surprise lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker grabbed a vital equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to complete a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past thirteen seasons.