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A new copper (II) ion-selective polymeric membrane electrode based on novel heteropolyacid salt named chromium (III) molybdotungstate, has been prepared. Ion exchange methodology was employed to synthesize chromium [III] molybdotungstate [CrMoW] and then structural aspects were deduced on the basis of instrumental techniques like IR, XRD, TGA, SEM and EDS analysis. On the basis of above analysis, the empirical formula of the amorphous CrMoW product was derived as [(Cr O ) (H MoO ) (H WO ) ]. 8H O with a molecular weight 1580. Physico-chemical description of this compound includes ion exchange capacity and distribution coefficient data. The prepared membrane showed excellent response in the concentration range of 1×10 M to 1×10 M +2 Cu ion with a sub-Nernstian slope of 9.2 mV/decade and -6 detection limit was up to 1×10 M. This analysis suggests that the prepared comppund is preferentially selective for 2+ Cu ion.