PSG has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice in the closing moments to take a shock lead. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past 13 years.
