Modification of copper (Cu) catalysts for enhanced carbon dioxide reduction (CO2R) is a long-standing challenge in the field of artificial photosynthesis. Altering Cu’s surface chemistry and material properties has been suggested as a route to alter the binding energies of CO2–° and CO* intermediates important for CO2 activation and reduction. However, producing materials that promote C-C bond coupling while limiting parasitic formation of H2 is a non-trivial matter. To address these challenges, we target a two-pronged approach. The first prong involves modification of Cu’s surface via interfacing with oxide overlayers. Synthesized via hydrothermal techniques directly onto Cu electrodes, the oxides investigated include porous aluminosilicate zeolites, tungsten oxide, and vanadium oxide, all of which impact copper’s ability to reduce CO2. The second prong involves Cu catalyst synthesis via electrochemically induced phase transition from Cu(II)-based nanostructured precursors. Results suggest that the initial morphology of the Cu precursors before electroreduction impacts the selectivity of products produced from CO2R. In all cases, materials were thoroughly characterized by X-ray and microscopy techniques and CO2R was conducted in a custom-built electrochemical, two-chamber compression cell. Further understanding of the structural and electronic properties of these materials will enable selectivity tuning in future CO2R electrocatalysts.