After the Premier League and FA Cup winners were locked at 1-1 following an evenly contested 90 minutes, the Frenchman stroked home after Alvaro Morata and Thibaut Courtois missed for Chelsea, in a shootout that trialled the new 'ABBA system'.
Chelsea's Victor Moses opened the scoring when he reacted fastest to smash a loose ball past Petr Cech in the 46th minute before Arsenal substitute Sead Kalasinac equalised in the 82nd minute, heading home to cap an impressive performance.
Chelsea's Pedro was dismissed for a nasty lunge on Mohamed Elneny which led to Arsenal's equaliser, while Arsene Wenger's side also handed a debut to record signing Alexandre Lacazette.
Chelsea begin their title defence when they host Burnley on Saturday, while Arsenal entertain Leicester City on Friday to kick off the Premier League season
At a sun-kissed Wembley, Arsenal, who beat Chelsea in May to win the FA Cup, started brightly with Lacazette, Danny Welbeck and Alex Iwobi all having early half-chances. Arsenal's fluid front three continued to cause the Premier League champions problems and midway through the half France forward Lacazette saw his curling effort cannon off the post.
Chelsea, who cantered to last season's league title, grew into the game and Spanish winger Pedro drew a save from Cech with a fearsome drive following a swift counter-attack.
Chelsea's Willian was then booked when referee Robert Madley judged the Brazilian to have dived as he surged past Hector Bellerin into the Arsenal box.
The second half was less than a minute old when Moses, sent off in the FA Cup final defeat, reacted fastest against a static Arsenal defence to thrash home Gary Cahill's header.
In response, Courtois had to be alert to beat away a fierce, goal-bound cross from Elneny and then a rasping long-range drive from Granit Xhaka before the impressive Kolasinac, a close-season signing from Schalke 04, nodded home a deserved equaliser.
Morata was brought on in the closing stages and the 24-year-old headed narrowly wide late on in what would have been the perfect introduction following his summer arrival from Spanish giants Real Madrid.
Cahill, scored for Chelsea to open the shootout, which was based on the ABBA format used in tennis tie-breaks.
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