The Parisian club has now claimed the prestigious trophy on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the French Cup winners after the French winger opened the net in the opening stages.
Yet, the southern French side fired twice late to take a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past thirteen years.
