The Parisian club has now claimed the prestigious cup on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired twice late to take a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past 13 seasons.