PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, the southern French side struck two times late to take a shock lead. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the past 13 years.
