The Parisian club has now secured the season-opening cup on fourteen separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the French Cup winners after the French winger opened the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to seize a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to seal a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
