The Parisian club has now claimed the season-opening cup on fourteen different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice late to take a surprise advantage. First, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the past 13 years.