PSG has now secured the prestigious cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the match between the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice late to seize a surprise advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial leveler in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past 13 years.
