PSG has now won the season-opening cup on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net early on.
However, the southern French side fired two times in the closing moments to seize a shock advantage. First, the English forward scored from the penalty spot, before the defender inadvertently 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 send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 years.
