PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown between the French league winners and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, Marseille fired two times in the closing moments to seize a surprise advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
