Abstract: The effect of NaNO₃ concentration on the anodic electrochemical behavior of antimony in 4 M NaOH solution was investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses. The mechanism of NO₃^- concentration effect on the anodic electrochemical behavior of antimony was proposed, and its availability was confirmed by experimental results. The effect of NaNO₃ on the anodic behavior of antimony in NaOH solution can be interpreted as a stepwise formation of different antimony compounds with different NaNO₃ concentrations. Metallic antimony is apt to be oxidized into Sb₂O₃ within the NaNO₃ concentration range of 0-0.48 M. NaSbO₃ can be found on the antimony surface when the NaNO₃ concentration increases gradually. Insoluable NaSbO₃ inhibits the anodic oxidation of antimony due to its shielding effect on the mass transport of the reactants and products. Surface morphology and composition were analyzed by X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM), and electron dispersion spectroscopy (EDS) analyses. Results indicate that the anodic oxidation layer is composed of Sb₂O₃, NaSbO₃, and Sb. The atomic proportion of antimony in the form of NaSbO₃ increases with increasing NaNO₃ concentration due to the powerful oxidizing property of NaNO₃.