PSG has now secured the season-opening cup on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the showdown between the French league champions and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille fired twice late to seize a surprise advantage. First, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial equaliser in the final moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last thirteen years.
