Polyaniline Zr(IV) molybdophosphate (PAZMP) was synthesized by sol-gel method and its ion exchange capacity (IEC) was determined as 2.50 meqg(-1). On the basis of distribution co-efficient (K-d values) the material was selective for Ni(II). The Ni(II) selective membrane was prepared (IEC 0.65 meqg(-1)) to fabricate Ni(II) selective membrane electrode with its linear potential response in the concentration range of 1 x 10(-7) M-1 x 10(-1) M. The morphology and composition of the prepared PAZMP membrane were ascertained by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) respectively. The ion exchange mechanism through membrane was determined by chronopotentiometric studies using Nernst-Planck equation at 30 degrees C, 45 degrees C and 60 degrees C. As a result physical parameters such as self-diffusion coefficient (D-o), energy of activation (E-a) and entropy of activation (Delta S degrees) were calculated. The analytical utility of this electrode was established by employing it as an indicator electrode in potentiometric titration. (C) 2013 Elsevier B.V. All rights reserved.