PSG has now won the prestigious cup on fourteen different occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the net early on.
However, Marseille struck twice late to take a surprise advantage. First, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to complete a convincing penalty victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past 13 years.
