Polyanilinezirconium(IV) arsenate composite cation exchange material was synthesized under different experimental conditions by the incorporation of polyaniline into the matrices of inorganic precipitate (zirconium(IV)arsenate). The experimental parameters such as concentration, mixing volume ratio, and pH were established for the synthesis of the material. Ion-exchange material that was synthesized at pH 1.0 showed an ion exchange capacity of 1.33 meq g-1 for Na+ ions. The composite material exhibits improved ion-exchange capacity along with chemical and thermal stability. The exchanger was characterized based on FTIR, TGA, XRD, and SEM analysis. The X-ray diffraction study shows semi-crystalline nature of the material. The distribution coefficient studies (Kd) of metal ions on the material were performed in diverse solvent systems. Based on Kd values the material was found to be selective for Pb(II) and Hg(II) ions. Some analytically important binary separations of metal ions in synthetic mixtures viz. Ba2+-Pb2+, Pb2+-Ni2+, Cd2+-Hg2+, Ni2+-Hg2+, Zn2+-Pb2+, Ca2+-Bi3+, Al3+-Hg2+, and Ca2+-Pb2+ were achieved on the columns of polyanilinezirconium(IV) arsenate cation exchanger. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012