This talk discusses the use of electrodeposition to make electrocatalysts. We show that electrodeposition of CuAg or CuSn alloy films under suitable conditions yields high surface area catalysts for the active and selective electroreduction of CO₂ to multi-carbon hydrocarbons and oxygenates. Alloy films containing Sn exhibit greater efficiency for CO production relative to either Cu along or CuAg at low overpotentials. In-situ Raman and electroanalysis studies suggest the origin of the high selectivity towards C₂ products to be a combined effect of the diminished stabilization of the Cu₂O overlayer and the optimal availability of the CO intermediate due to the Ag or Sn incorporated in the alloy. Sn-containing films exhibit less Cu₂O relative to either the Ag-containing or neat Cu films, likely due to the increased oxophilicity of the admixed Sn. Incorporation of a polymer into the Cu electrodeposit leads to very active CO₂ reduction electrocatalysis due to pH changes at the electrified interface. Vibrational spectroscopy is used to evaluate the pH at the interface during electrolyzer operation. Co-electrodeposition of polymers with other metals yields active electrocatalysts for other processes.