PSG has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to seize a surprise advantage. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who faced 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 past 13 seasons.