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The electrochemical CO 2 reduction reaction (CO 2 RR) to produce methanol (CH 3 OH) is an attractive yet challenging approach due to a lack of selective electrocatalysts. An immobilized cobalt phthalocyanine (CoPc) molecular catalyst has emerged as a promising electrocatalyst for CH 3 OH synthesis, demonstrating decent activity and selectivity through a CO 2 -CO-CH 3 OH cascade reaction. However, CoPc's performance is limited by its weak binding strength toward the CO intermediate. Recent advancements in molecular modification aimed at enhancing CO intermediate binding have shown great promise in improving CO 2 -to-CH 3 OH performance. In this Perspective, we discuss the competitive binding mechanism between CO 2 and CO that hinders CH 3 OH formation and summarize effective molecular modification strategies that can enhance both the binding of the CO intermediate and the conversion of the CO 2 -to-CH 3 OH activity. Finally, we offer future perspectives on optimization strategies to inspire further research efforts to fully unlock the potential for methanol synthesis via the CO 2 RR using molecular catalysts.