PSG has now won the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net early on.
However, Marseille fired twice in the closing moments to seize a shock lead. First, Mason Greenwood 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 moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past thirteen years.
