PSG has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider 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 win in the match featuring the Ligue 1 winners and the Coupe de France winners after the French winger opened the net in the opening stages.
However, the southern French side fired twice in the closing moments to take a surprise advantage. 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 remarkable turn of events, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.
