The development of efficient catalysts is one of the main challenges in CO conversion to valuable chemicals and fuels. Herein, inspired by the knowledge of the thermocatalytic (TC) processes, Cu/ZnO and bare Cu catalysts enriched with Cu were studied to convert CO via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO reduction to reduce the kinetic barrier and enhance C-C coupling to obtain C chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·g·h in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C products like formate and methanol. During CO hydrogenation, a methanol selectivity close to 100% was achieved with the Cu/ZnO catalysts at 200 °C, a value that decreased at higher temperatures (i.e., 23% at 300 °C) because of thermodynamic limitations. The methanol productivity increased to approximately 1.4 mmol·g·h at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu/Cu interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu and crystalline ZnO prevailed under CO hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu catalyst surface in the TC process than in the Cu present in the EC one leads to preferential CO and methanol production in the TC system. Instead, our EC results revealed that an optimum local CO production at the ZnO surface in tandem with a high amount of superficial Cu + Cu species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO conversion products.