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Electrocatalytic CO2reduction to high-value chemicals has significant potential to combat environmental and energy crises. The strength and mode of adsorption of reaction species play a crucial role in determining the CO2reduction products. Therefore, it is vital to construct catalytic interfaces with high catalytic activity, selectivity and chemically homogeneous for efficient CO2reduction. Herein, ultra-thin carbon layer encapsulated sub-5 nm SnO2quantum dots (SnO2@u-C) has been prepared by Sn-MOFs derivation for efficient electrocatalytic CO2reduction. Specifically, the Faradaic efficiency of formate (FEformate) and energy efficiency of formate production (EEformate) exceed 80% and 50% respectively, over a wide potential range, with the highest value reaching 95.7% for FEformateand 58.2% for EEformate. Moreover, SnO2@u-C electrode shows excellent stability over 10h with FEformateabout 89% at −1.17V versus reversible hydrogen electrode. DFT calculations and experimental characterization reveal that the ultrathin carbon layer coating on the surface of SnO2forms a chemically homogeneous catalytic interface, facilitating the adsorption and conversion of reaction species to achieve exceptional formate selectivity. Moreover, the carbon layer builds a three-dimensional rapid electron conduction network that supports electron transfer to CO2molecules and suppressing SnO2reduction.