PSG has now claimed the prestigious cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a surprise advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, 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 convincing shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the last thirteen seasons.
