The increased awareness of carbon management has prompted the scientific community towards delivering sustainable catalytic technologies, preferably from CO2. Copper-based multifunctional catalysts are the most frequently used for thermal hydrogenation and electrocatalytic reduction of CO2 (CO2R) processes. To improve the understanding and efficacy of these materials for the CO2R reaction, Cu-Zn oxides combined with Al2O3 and ZrO2 were synthesized by the coprecipitation method and annealed at 500 °C, 600 °C, and 700 °C (i.e., Cu/ZnO/Al2O3-x and Cu/ZnO/ZrO2 systems-x, where x is the annealing temperature) to tune their multi-functionality. We demonstrate that the composition of Cu-Zn oxides and pretreatment temperature impact the electrocatalytic CO2R performance, where CuZnZr-600 and CuZnAl-700 materials are superior. Different characterization tools were employed to rationalize the results described in this work, which could provide a way to design an efficient catalytic system for the CO2R process.