AbstractElectrochemical CO2 reduction reaction (CO2RR) holds a great potential for converting CO2 into valuable carbon‐based chemicals and fuels. A promising strategy for enhancing CO2RR performance is the deliberate structural design of electrocatalysts, which can maximize the utilization of inherent structural advantages. In this work, SnO2 nanocubes (NCs) and nanorods (NRs) are synthesized using a surface energy‐driven growth orientation method, where the stable (110) facet and the highly energetic (001) facet constitute the SnO2 nanostructures. Leveraging the inherent structural merits of different facets on SnO2, theoretical calculations reveal that the (001) facet plays a primary role in inhibiting hydrogen evolution reaction (HER), while both (110) and (001) facets are highly favorable for CO2‐to‐formate conversion under the external bias. As a result, SnO2 NCs with a higher facet ratio of (001)/(110) achieve nearly 100% selectivity for the formation of carbonaceous products during CO2RR. More importantly, a maximum partial current density of about 1 A cm−2 with a formate Faradaic efficiency (FE) of over 90% is achieved in a flow cell, distinguishing it from most of the reported Sn‐based electrocatalysts. These results highlight the strategic advantages of leveraging the inherent structure of nanomaterials for efficient CO2RR.