Many technical challenges remain for the implementation of CO₂ electrolysis as a practical means for CO₂ utilization. Here, we outline strategies for improving the performance of catalysts for the electroreduction of CO₂ to oxygenated and multicarbon reduction products. To this end, we will first discuss how engineering the surface structure of Cu electrocatalysts led to the discovery of active site structure-selectivity relationships. Using a combination of electrocatalysis experiments and in situ surface probe microscopy, we demonstrate that undercoordinated sites are selective motifs for oxygenates and C-C coupling. By comparing these results with state-of-the-art Cu electrocatalysts from the literature, we show that different morphologies have similar intrinsic activities for CO₂ reduction. Afterwards, we will discuss a tandem catalysis approach for improving upon these normalized CO₂ reduction activities, which is enabled by utilizing bimetallic electrodes consisting of Au nanoparticles on polycrystalline Cu (Au/Cu). At low overpotentials, the Au/Cu electrocatalyst has a synergistic catalytic activity superior to that of either Cu or Au, indicating that tandem catalysis mechanisms can be utilized to increase the energy efficiency for alcohol production. By comparing Au/Cu to Cu, we highlight common potential-driven trends in the selectivity to oxygenated and multicarbon products, providing insights on how to develop new electrocatalysts that can guide selectivity to valuable chemicals and fuels.