This study was performed to investigate the separation of cesium cations by using an electrochemical ion exchanger of nickel hexacyanoferrate($KNiFe(CN)_6$) film electrode. Potential, current, and charge passing through the cyclic voltammograms were measured in singular and binary solutions of 1.0M $NaNO_3$ and 1.0M $CsNO_3$. Before and after each experiment, the structural morphology and atomic composition of $KNiFe(CN)_6$ were analyzed by SEM and EDS, respectively. The ion selectivity of $KNiFe(CN)_6$ was also observed by the voltammograms and atomic compositions measured in the solution alternated between sodium and cesium. As the result of this study, it was found that the electrically switched $KNiFe(CN)_6$ ion exchanger had the significant advantage of 40 times or longer durability than conventional organic or inorganic ion exchanger. It was also shown that the $KNiFe(CN)_6$ ion exchanger had high selectivity for cesium over sodium.