Polypyrrole composite cation- and anion-exchange membranes (CEM and AEM), in which polypyrrole (PPY) coated on one surface of the membrane as a thin layer, were prepared by chemical polymerization of pyrrole in the presence of high oxidant concentration (Na2S2O8). Existence of polypyrrole layer on the both types of ion-exchange membranes were confirmed by recording their coating density, SEM images and conductivity. These membranes were extensively characterized by recording their properties such as water uptake, ion-exchange capacity, contact angle, permselectivity and membrane conductivity as a function of polymerization time such as. It was observed that due to coating of PPY for 2 h, membrane permselectivity of CEM for NaCI (0.907) was reduced to 0.873, while it was increased from 0.747 to 0.889 in the case of AEM. Similar behaviors were also obtained for bi-valent electrolytes. Electrodialysis experiments were also conducted with polypyrrole composite ion-exchange membranes using mixed electrolytic systems. Relative dialytic rates for NaCl with respect to other bi-valent electrolyte were varied in between 5 and 8 (depending on bi-valent electrolyte), which suggested the feasible and efficient separation of mono-valent from bi-valent electrolyte. Slower electro-migration of bi-valent electrolyte (CaCl2, MgCl2 and CuCl2) in comparison to NaCl was explained on the basis of synergetic effect of sieving of bulkier bi-valent cations by tight and rigid polypyrrole layer and the difference in electrostatic and hydrophobic-hydrophilic repulsion force between bi-valent cations and mono-valent cation. It was concluded that these composite membranes are suitable for the efficient separation of same type of charged ions by electro-driven separation techniques. (c) 2006 Elsevier B.V. All rights reserved.