Nigeria international Victor Moses stabbed the ball home on 47 minutes for Chelsea, but Arsenal equalised nine minutes from time through new signing from Schalke, Sead Kolasinac.
Chelsea finished the game with 10 players after a red card for Pedro and along with Moses he will now miss the start English Premier League season next weekend against Burnley.
The match went to penalties, which were conducted in the new ‘ABBA’ format that saw Chelsea go first, with Arsenal then taking the next two, and Chelsea the two after that.
Gary Cahill netted Chelsea’s first, but when Thibaut Courtois and Alvaro Morata missed with their next two, Arsenal were able to complete the job.
Gunners forward Alexandre Lacazette twice went close in the opening stages, first seeing his shot blocked after good work from Alex Iwobi, and then curling an effort against the post.
Chelsea thought they should have had a penalty when Willian tumbled in the box after a tussle with Hector Bellerin, but the former was booked for simulation, harsh given that he essentially tripped over his own feet.
Chelsea had the lead just after halftime when Granit Xhaka’s attempt at a clearance went high into the air and was flicked by Gary Cahill into the path of Moses, who finished from close-range.
Cesc Fabregas and Michy Batshuayi both went close for Chelsea soon afterwards as they began to take a grip on the game, but in the closing stages things turned in Arsenal’s favour.
Xhaka forced a fine save from Courtois with 15 minutes remaining as The Gunners searched for an equaliser. And they then found themselves a man up as Pedro received a deserved red card for a ‘studs-up’ challenge on Mohamed Elneny.
From the resultant free-kick, Kolasinac headed Arsenal level with nine minutes remaining to send the game to spot-kicks.
Arsenal at Wembley since 2014: Played: 9 Won: 9 Lost: 0 Trophies: 4
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