Electrocatalytic CO2 reduction 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 CO2 reduction products. Therefore, it is vital to construct catalytic interfaces with high catalytic activity, selectivity and chemically homogeneous for efficient CO2 reduction. Herein, ultra-thin carbon layer encapsulated sub-5 nm SnO2 quantum dots (SnO2@u-C) has been prepared by Sn-MOFs derivation for efficient electrocatalytic CO2 reduction. 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 FEformate and 58.2 % for EEformate. Moreover, SnO2@u-C electrode shows excellent stability over 10 h with FEformate about 89 % at −1.17 V versus reversible hydrogen electrode. DFT calculations and experimental characterization reveal that the ultrathin carbon layer coating on the surface of SnO2 forms 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 CO2 molecules and suppressing SnO2 reduction.