PSG has now secured the season-opening trophy on fourteen different times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice late to seize a surprise lead. Initially, the English forward converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the past thirteen years.