PSG has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck two times late to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital leveler in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past thirteen years.