PSG has now claimed the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille fired twice in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing penalty win.
The record winners PSG, 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 twelfth time in the last 13 seasons.
