PSG has now won the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, Marseille fired two times in the closing moments to seize a surprise advantage. First, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned 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 moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, 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 last thirteen seasons.
