Significance Anthropogenic global warming necessitates the development of renewable carbon-free and carbon-neutral technologies for the future. Electrochemical CO ₂ reduction is one such technology that has the potential to impact climate change by enabling sustainable routes for the production of fuels and chemicals. Whereas the field of CO ₂ reduction has attracted great interest, current state-of-the-art electrocatalysts must be improved in product selectivity and energy efficiency to make this pathway viable for the future. Here, we investigate how controlling the surface structure of copper electrocatalysts can guide CO ₂ reduction activity and selectivity. We show how the coordination environment of Cu surfaces influences oxygenate vs. hydrocarbon formation, providing insights on how to improve selectivity and energy efficiency toward more valuable CO ₂ reduction products.