Alternating square-wave current electrolysis using a Na2SO4 electrolyte was studied as a removal method for radioactive contaminated oxidation film on metal surfaces. After the oxidation film was selectively removed using the Na2SO4 electrolyte, base metal was removed. Based on a diffusion model in which the removal rate of the surface oxidation film depends on the diffusion rates of O2- and Fe2+ ions in the film, the optimum cycle of the alternating square current was estimated to be 90 s (the square widths of the negative and positive currents were 60 and 30 s, respectively). The theoretical estimation was in good agreement with the experiment results. Using this decontamination method, decontamination factors of 101 to 104 were obtained for stainless steels of a boiling water reactor coolant system and radioactive simulated samples.