The Parisian club has now claimed the prestigious cup on fourteen separate occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, the southern French side fired twice in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital equaliser in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.