The selective autoxidation for the synthesis of valuable oxygenates has provoked keen interest from both academic and industrial sectors. Although the generation of reactive oxygen species via oxygen attack on C─H bonds near ester linkages is well-established, research into aliphatic ester oxidation has primarily focused on combustion, neglecting their potential utility in oxidation processes. Herein, a protocol for producing propylene oxide through the autoxidation of ethyl acetate in tandem with propylene epoxidation is demonstrated. The ethoxy radical, generated by ester C(acyl)─O bond cleavage in situ, subsequently underwent proton-coupled electron transfer with the Co(OAc)(μ-H