PSG has now secured the season-opening cup on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown featuring the French league winners and the French Cup winners after the French winger opened the net early on.
Yet, the southern French side struck two times in the closing moments to take a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital equaliser in the final seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.