PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown featuring the French league winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, the southern French side fired two times late to seize a shock lead. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last thirteen years.
