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Electrochemical 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. [ABSTRACT FROM AUTHOR]

The construction of an interface has been demonstrated as one of the most insightful strategies for designing efficient catalysts toward electrochemical CO2 reduction (CO2RR). However, the weak interfacial interaction and inherent instability inevitably hinder a further performance enhancement in CO2RR attributable to the interface effect. Herein, 2 nm Ag nanoclusters (Ag NCs) are embedded onto CeO2 nanospheres (CeO2 NSs) with highly interconnected porosity (Ag NCs@CeO2 NSs) to exclusively study the pure interface effect toward CO2RR. The enhanced Ag–CeO2 pure interface endows Ag NCs@CeO2 NSs with a remarkably larger current density, significantly higher Faraday efficiency (FE), and energy efficiency as compared to Ag NCs, CeO2 NSs, and the one with Ag NCs dispersed on CeO2 nanoparticles. More importantly, an impressively high CO FE of over 70.0% is achieved at an ultralow overpotential (η) of 146 mV. The free energy and differential charge calculations, coupled with X‐ray photoelectron spectroscopy results jointly imply that the effective initiation of CO2RR to CO at a lower η over Ag NCs@CeO2 NSs derives from the enhanced interface‐induced charge delocalization, which enhances the electron transfer ability toward *COOH intermediate, thus overcoming the energy barrier demanded for the rate‐determining step. [ABSTRACT FROM AUTHOR]