PSG has now claimed the season-opening trophy on 14 different times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a straightforward win 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 two times late to seize a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 years.
