PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net early on.
However, the southern French side fired twice late to take a surprise lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial equaliser in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen seasons.