PSG has now secured the season-opening trophy on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, Marseille fired two times in the closing moments to seize a surprise lead. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial leveler in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
