PSG has now secured the prestigious trophy on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille fired twice late to take a shock lead. First, the English forward 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, Goncalo Ramos snatched a crucial leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 years.