Herein, we demonstrate the successful utilization of copper catalysis and oxygen oxidation for consecutive C(sp 3 )-C(sp 3 ) bond cleavage in alkyl cyclic ethers. A key step involves a copper-oxygen autoxidation process, generating in situ alkoxy radicals and triggering sequential C-C bond cleavage. This β-oxidative cleavage strategy enables the use of cyclic ethers as valuable C1 building blocks for the synthesis of bridged methylene dimers. This reaction holds promise for inspiring alternative methods targeting inert C(sp 3 )-C(sp 3 ) bond cleavage.