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While converting carbon dioxide (CO2) into value-added carbon products by electrolyzing offers a promising approach to mitigate global warming and store energy, poor selectivity and stability of catalysts still impede this conversion. Single-atom catalyst exhibits exceptional selectivity for CO2 electroreduction reaction in response to inhibiting hydrogen evolution reaction (HER), which is the major obstacle to the development of CO2 reduction. Herein we introduce a facile approach to obtain Ni-Nx sites encapsulating into carbon nanotubes with a nickel loading as high as 6.63 wt%. This catalyst exhibits high Faradaic efficiency approximately 95% for CO2 electroreduction to carbon monoxide (CO) in the wide potential range from −0.7 to −1.0 V, and the current density reaches 57.1 mA cm−2 at −1.0 V versus a reversible hydrogen electrode (RHE). Experiments and characterization results demonstrate that nickel chemical state and content play a vital role for CO2 electrocatalytic performance. Moreover, the simplifying of the synthesis may shed a new light on design single atom catalysts of electrochemistry in addition to CO2 reduction.