A novel electrochemical adsorption system using a nanoparticle film of copper (II) hexacyanoferrate (III) was proposed for selectively removing cesium from wastewater. This system can be used for cesium separation without extra chemical reagents or any filtration treatment. Cesium uptake and elution can be simply controlled by switching the applied potentials between anodes and cathodes. Data from batch kinetic studies well fitted the intraparticle diffusion equation, reflecting a two-step process: a steepest ascent portion followed by a plateau extending to the equilibrium. The effective cesium removal with a high distribution coefficient (K-d > 5 x 10(5) mL/g) can be adopted in a large pH range from 0.3 to 9.2, and in the presence of several diverse coexisting alkaline cations, suggesting it can be taken as a promising technology for actual nuclear wastewater treatment. (C) 2012 Elsevier Ltd. All rights reserved.