The Parisian club has now secured the prestigious cup on fourteen 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 European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, Marseille fired two times in the closing moments to take a surprise lead. 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 events, the Portuguese striker grabbed a vital leveler in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
