<p>The electrochemical reduction of carbon dioxide (ECO₂RR) into ethanol is a hopeful route for carbon neutrality through the production of value-rich carbon-based fuels. Yet, low selectivity toward ethanol is a critical challenge for its realization. In this review, recent advancements toward improving ethanol selectivity are critically discussed through the synthesis of hybrid catalysts as well as strategic process design. We review critical roles of copper-based nano-architectures, bimetallic, and MOF-templated electrocatalysts, focusing on their structure-property relationships and their interfacial chemical bonds with key intermediates. Further, the impacts of electrolytes, reaction environments, and optimized reactor designs on product selectivity are discussed comprehensively. Particular emphasis is placed on synergistic strategies where atomic-level tuning of the catalyst is integrated with macro-scale optimization of the system, allowing for over 70% Faradaic efficiency (FE), for instance. By bridging basic scientific concepts with engineering achievements, the review provides a framework for scalable, efficient, and green ethanol production from CO₂, supporting international carbon neutrality goals as well as next-generation energy demands.&#xa0;</p> Graphical Abstract <p></p>