Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed a new catalytic system that integrates photoinduced hydrogen atom transfer (HAT) and chiral copper catalysis, involving the fine-tuning of chiral ligands, additives, and other reaction parameters. The strategy facilitates regiodivergent and enantioselective cross-couplings between N-aryl glycine ester/amide derivatives and abundant hydrocarbon feedstocks through strong C(sp3)-H bond activation. This approach allows for the controlled and stereoselective formation of C(sp3)-C(sp3) and C(sp3)-N bonds, yielding a rich variety of C- or N-alkylated glycine esters and amides with commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), and high enantioselectivities (up to 96% ee). Our methodology not only provides a promising avenue for the stereoselective incorporation of alkyl functionalities onto specific sites of biologically significant molecules but also offers a practical approach for regioselectivity switching while simultaneously achieving high asymmetric induction within photochemical reactions.