PSG has now claimed the prestigious cup on 14 different times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the French league winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, Marseille struck twice late to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the final seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 years.
