Copper Cobalt Selenide, CuCo2Se4, Has Been Identified as an Efficient Catalyst for Electrocatalytic CO2 Reduction, Exhibiting High Selectivity for Carbon-Rich and Value-Added Products. Achieving Product Selectivity is One of the Primary Challenges for CO2 Reduction Reactions, and the Catalyst Surface Plays a Pivotal Role in Determining the Reaction Pathway And, More Importantly, the Intermediate Adsorption Kinetics Leading to C1- or C2+-Based Products. in This Research, the Catalyst Surface Was Designed to Optimize the Adsorption of the Intermediate CO (Carbonyl) Group on the Catalytic Site Such that its Dwell Time on the Surface Was Long Enough for Further Reduction to Carbon-Rich Products But Not Strong Enough for Surface Passivation and Poisoning. CuCo2Se4 Was Synthesized through Hydrothermal Method, and the Assembled Electrode Showed the Electrocatalytic Reduction of CO2 at Various Applied Potentials Ranging from −0.1 to −0.9 V vs. RHE. More Importantly, It Was Observed that the CuCo2Se4-Modified Electrode Could Produce Exclusive C2 Products Such as Acetic Acid and Ethanol with 100% Faradaic Efficiency at a Lower Applied Potential (−0.1 to −0.3 V), While C1 Products Such as Formic Acid and Methanol Were Obtained at Higher Applied Potentials (−0.9 V). Such High Selectivity and Preference for Acetic Acid and Ethanol Formation Highlight the Novelty of This Catalyst. the Catalyst Surface Was Also Probed through Density Functional Theory (DFT) Calculations, and the High Selectivity for C2 Product Formation Could Be Attributed to the Optimal CO Adsorption Energy on the Catalytic Site. It Was Further Estimated that the Cu Site Showed a Better Catalytic Activity Than Co; However, the Presence of Neighboring Co Atoms with the Residual Magnetic Moment on the Surface and Subsurface Layers Influenced the Charge Density Redistribution on the Catalytic Site after Intermediate CO Adsorption. in Addition to CO2 Reduction, This Catalytic Site Was Also Active for Alcohol Oxidation Producing Formic or Acetic Acid from Methanol or Ethanol, Respectively, in the Anodic Chamber. This Report Not Only Illustrates the Highly Efficient Catalytic Activity of CuCo2Se4 for CO2 Reduction with High Product Selectivity But Also Offers a Proper Insight of the Catalyst Surface Design and How to Obtain Such High Selectivity, Thereby Providing Knowledge that Can Be Transformative for the Field.