The lack of availability of efficient, selective and stable electrocatalysts is a major hindrance for scalable CO2 reduction processes. Herein, we report the generation of Cu–In alloy surfaces for electrochemical reduction of CO2 from mixed metal oxides of CuInO2 as the starting material. The material successfully generates selective active sites to form CO from CO2 electroreduction at mild overpotentials. Density functional theory (DFT) indicates that the site occupation of the inert In occurs more on the specific sites of Cu. In addition, while In atoms do not preferentially adsorb H or CO, Cu atoms, which neighbor the In atoms, alters the preference of their adsorption. This preference for site occupation and altered adsorption may account for the improved selectivity over that observed for Cu metal. This study demonstrates an example of a scalable synthesis method of bimetallic surfaces utilized with the mixed oxide precursor having the diversity of metal choice, which may drastically alter the electrocatalytic performance, as presented herein.