PSG has now won the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen years.
