PSG has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net early on.
Yet, Marseille struck twice late to seize a surprise lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a vital leveler in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 years.