An alternating current paired photo-electrocatalysis approach, integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis, enables enantioselective C(sp3)–C(sp2) cross-coupling of alcohols. This approach has high catalytic efficiency and stability, achieving up to 99% enantiomeric excess with broad substrate compatibility, and is suitable for late-stage functionalization of complex molecules.