A copper-photocatalyzed dealkylation of aryl alkyl ethers is established by using O2 as an oxidant. This methodology demonstrates exceptional practicality through mild reaction conditions, an economical and stable catalytic system, operational simplicity, high conversion efficiency, scalability to 10 g, and broad substrate generality. Mechanistic investigations reveal that the chlorine radical mediates substrate activation, followed by oxidation and hydrolysis to achieve dealkylation. This mild and efficient method can be a competitive alternative for aryl ether deprotection.