PSG has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side struck twice late to take a surprise advantage. 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 remarkable twist of events, the Portuguese striker grabbed a vital leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the last thirteen years.
