Abstract Electrochemical reduction of carbon dioxide to formate provides an effective way to solve the environmental problems caused by excessive carbon dioxide emissions and produce value‐added products. Herein, we report the preparation of a Sn‐doped CeO 2 catalyst, where oxygen vacancies are formed by thermal treatment in Ar/H 2 atmosphere, leading to enhanced carbon dioxide electroreduction to formate. The Faraday efficiency of formate production is found to reach 81.10 %, with a geometric current density of 9.13 mA cm −2 at a potential of −1.10 V versus reversible hydrogen electrode. Density functional theory calculations show that the incorporation of tin into CeO 2 promotes electron transport, lowers the energy barrier to form formate through HCOO*, and increases the selectivity of formate. Results from this study highlight the importance of metal‐doping in CeO 2 towards the selective reduction of CO 2 to formate.