PSG has now claimed the prestigious trophy on fourteen different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net early on.
However, the southern French side fired two times in the closing moments to take a surprise lead. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the dying seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
