PSG has now claimed the prestigious cup on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward win in the match featuring the French league champions and the French Cup holders after the French winger found the net in the opening stages.
Yet, the southern French side fired twice late to take a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the last 13 years.
