A goal from Alex Oxlade-Chamberlain in the first half settled the all-London affair and gave Arsene Wenger his first victory over Chelsea manager Jose Mourinho in 14 meetings.
It was also a sweet moment for 33-year-old Petr Cech, keeping a clean sheet against his old club following his $15.6 million move to the Gunners this summer.
He was rarely called into action as Chelsea failed to make much impression against the Arsenal defense, but made a fine save to keep out Oscar’s second half free kick and looked assured in claiming several testing crosses in a tense finish.
Arsenal had last been at Wembley back in May when it won the FA Cup and Wenger’s men made the better start with Theo Walcott proving a nuisance in the central striking role.
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The England international set up 21-year-old Oxlade-Chamberlain for his 24th minute goal, the winger cutting past Cesar Azpilicueta before beating Thibaut Courtois with a strong shot.
Mourinho brought on new signing Radamel Falcao for Loic Remy after the break, but the Colombian failed to sparkle and the Blues were clearly missing the injured Diego Costa up front.
It was Arsenal that almost increased its lead in the closing stages when Santi Cazorla’s shot was saved by Courtois and Aaron Ramsey’s follow-up was blocked.
Kieron Gibbs was also denied by Courtois just before the final whistle.
The EPL season starts next weekend with Chelsea and Arsenal due to meet in league action on September 19.