Electroreduction of CO2into liquid fuels is a compelling strategy for storing intermittent renewable energy. Here, we introduce a family of facet-defined dilute copper alloy nanocrystals as catalysts to improve the electrosynthesis of n-propanol from CO2and H2O. We show that substituting a dilute amount of weak-CO-binding metals into the Cu(100) surface improves CO2-to-n-propanol activity and selectivity by modifying the electronic structure of catalysts to facilitate C1–C2coupling while preserving the (100)-like 4-fold Cu ensembles which favor C1–C1coupling. With the Au0.02Cu0.98champion catalyst, we achieve an n-propanol Faradaic efficiency of 18.2 ± 0.3% at a low potential of −0.41 V versus the reversible hydrogen electrode and a peak production rate of 16.6 mA·cm–2. This study demonstrates that shape-controlled dilute-metal-alloy nanocrystals represent a new frontier in electrocatalyst design, and precise control of the host and minority metal distributions is crucial for elucidating structure–composition–property relationships and attaining superior catalytic performance.