PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be sailing towards a comfortable triumph in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice late to seize a shock lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
