The Parisian club has now secured the season-opening cup on fourteen separate times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the scoring early on.
However, the southern French side struck two times in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past thirteen years.