Abstract: The MnHCF film electrodes of ITO substrate were prepared by cyclic voltammetry electrodeposition. The surface morphology and composition of the films were characterized by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and infrared spectroscopy(IR). And the optimal conditions for electrodeposition of film electrodes were detemined by combining with cyclic voltammetric curves of electrodeposition. The optimal conditions for electrodeposition of film electrodes are as follows: scan potential range -0.2-0.85 V, cycle number 50+50, scan rate 25 mV/s. The film electrodes has reversible electrochemical behavior in 1 mol/L NaNO₃ solution, and Na⁺ can reversibly intercalate into and deintercalate from the film electrodes under cyclic voltammetric conditions. Cs⁺ separation capacity of the films is investigated preliminarily. Experimental results show that it is good for separating Cs⁺and the removal rate of Cs⁺ reaches 64.98% by applying -0.2 V to oxidation state films. It provides reference for applying MnHCF film electrodes in treatments of liquid radioactive waste.