<p>The enantioselective transformation of alcohols into three-dimensional chiral molecules via C–C bond cleavage remains a substantial challenge in synthetic chemistry. In this study, an amino alcohol was used as a coupling partner to achieve asymmetric C(<i>sp</i>³)–C(<i>sp</i>²) cross-coupling by integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis. Notably, this work represents the application of alternating current in paired photo-electrocatalysis, substantially enhancing the reactivity of photo-electrochemical reactions. This approach disrupts the electrostatic interactions that anchor transition metal complexes within the electric double layer, preventing their accumulation on electrode surfaces and thereby improving catalytic efficiency, stability and long-term system performance. The platform accommodates a broad range of substrates, achieving exceptional enantioselectivities up to 99% enantiomeric excess and enabling late-stage diversification of complex, medicinally relevant molecules. Both experimental investigations and density functional theory calculations provide insights into the reaction mechanism and the origin of enantioselectivity in the asymmetric cross-coupling of alcohols.</p><p></p>