Nanoparticle (NPs) film of copper hexacyanoferrate (CuHCF(III)) was developed for electrochemically cesium separation from wastewater. Different form the electro- or chemical deposited films, CuHCF(III) NPs were firstly covered with ferrocyanide anions, so that they can be well dispersed in water and formed ink. Then CuHCF(III) NPs can be uniformly coated by simple wet printing methods, so it is feasible to prepare NPs film of any sizes, or any patterns at low cost. This process provided a promising technology for preparing large scale electrodes for sequential removal of Cs from wastewater in the columns. Cs separation can be controlled by an electrically switched ion exchange (ESIX) system. Effect of temperatures, and ionic strength on Cs removal was investigated. Thermodynamics results showed that Cs adsorption process was exothermic in nature and favored at low temperature. Ionic strength study indicated the CuHCF(III) film can selectively separate Cs in wide ionic strength range from 1 × 10(-4) to 1 × 10(-1) M Na(+). XPS results demonstrated that the electrochemical oxidation-reduction of Fe (II/III) made contributions to Cs separation.