PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, the southern French side fired two times in the closing moments to take a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the contest 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, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 years.
