In the present study, a polyvinyl chloride-based barium tungstate ion-exchange membrane was synthesized by sol–gel method. The structure of membrane was studied in terms of Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. X-ray diffraction analysis confirms crystalline form of the composite membrane without any other impurity. Scanning electron microscopy and Fourier transform infrared spectroscopy analysis show the uniform arrangement of particles in the membrane with crack-free surface structure and presence of different functional groups of the organic-inorganic materials. The electrochemical properties like surface charge density ( D), transport number and mobility ratio of the ion-exchange composite membrane were theoretically evaluated and compared with observed values using “Teorell, Meyers and Sievers” method. Transport number follows the order as KCl <NaCl < LiCl < NH4Cl, while the surface charge density showed reversed order. The results showed that the low concentration of electrolytes favors the high mobility of univalent cation in the present study. The above result proves the analytical utility of polyvinyl chloride-based barium tungstate ion-exchange membrane in environmental management.