The development of robust catalysts is a key challenge for sustainable CO₂ conversion into value-added chemicals. Herein, bimetallic copper phyllosilicate (CuPS) catalysts were developed and systematically compared with monometallic one for liquid-phase selective hydrogenation of CO₂ to alcohols. Among these, Mg-modified CuPS exhibited the highest activity with 98% selectivity of alcohol, stability, and reusability. Its superior performance is attributed to enhanced surface basicity and stronger CO₂ adsorption, which facilitate the formation and stabilization of formate intermediates, together with in-situ generation of Cu⁺/Cu⁰ sites that promote efficient H₂ dissociation. A high surface Mg/Si ratio further stabilizes CO-derived intermediates and enhances CO-mediated C-C coupling, favoring higher alcohol formation. Zn modification showed similar but weaker effects, while Pt altered the reaction network, inducing side reactions and lowering alcohol selectivity. Overall, Mg emerges as an earth-abundant and industrially viable promoter for CuPS catalysts in CO₂-to-alcohol conversion.