PSG has now claimed the prestigious cup on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice late to seize a surprise lead. Initially, the English forward converted 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 crucial leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
