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The electrochemical reduction of CO2 (CO2RR) is a versatile method that is capable of simultaneously reduce CO2 emission and produce valuable fuels and chemicals. However, its application is hindered by the lack of cost‐effective catalysts and significant overpotential requirement. In this work, we report a low‐cost and surfactant/capping agent free method to synthesize cubic Cu2O−SnO2 core‐shell electrocatalyst, whose thickness can be easily controlled by the content of tin precursor. The optimized Cu2O−SnO2 catalyst with a 5 nm‐thick shell achieved over 90 % faradaic efficiency towards CO at a low overpotential of 390 mV, which is comparable to some of the noble metal catalysts. The catalyst also exhibited good stability over 18 hours of test at −0.6 V vs. RHE in 0.5 M KHCO3 electrolyte. This work provides a widely applicable strategy for developing a low‐cost electrocatalyst for CO2 conversion. [ABSTRACT FROM AUTHOR]