PSG has now claimed the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after the French winger opened the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital equaliser in the dying moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a convincing shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last thirteen years.
