PSG has now secured the prestigious cup on fourteen separate occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the French Cup winners after the French winger opened the net early on.
However, the southern French side struck two times in the closing moments to take a surprise advantage. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last thirteen seasons.
