On the basis of our experimental findings, DFT calculations, and literature reports we propose that the enantioselective oxidative coupling of C(sp 3 )-H with carboxylic acids proceed by the mechanism shown in Fig. . In the reaction, irradiation decomposes DTBP to tert-butoxy radicals, which react with Cu I complex to form Cu II In summary, we have developed a cationic copper catalysis approach that enables the enantioselective oxidative coupling of allylic and propargyl C(sp 3 )-H bonds with carboxylic acids under blue light. This method not only broadens the asymmetric Kharasch reaction to encompass open-chain alkenes and alkynes, but also eliminates the need for peroxy esters as oxygen nucleophiles. Utilizing this method, we successfully synthesized various chiral esters directly from readily accessible C(sp 3 )-H substrates, achieving good to high enantioselectivities. Our research opens new avenues for the asymmetric functionalization of unactivated C(sp 3 )-H bonds. Furthermore, the identification of Cu III intermediate not only deepens understanding of coppercatalyzed reaction but also lays a solid foundation for its exploration and application in a wide field of chemistry.