PVC incorporated ZT/ZM composite materials have been synthesized via qualitative sol–gel method of material synthesis. Both the composite materials have the combination of inorganic ion-exchanger of different metal salt as well as same organic polymers, which is used to design a new class of organic–inorganic composite ion exchange membrane with much better chemical and mechanical properties, good ion-exchange capacity, higher thermal stability, reproducibility, selectivity etc. The physicochemical, electrochemical, mechanical and thermal properties of both the membranes were characterized by SEM, XRD, FTIR and simultaneous TGA–DTA studies were carried out to understand the ion exchange behavior of materials. The above analysis demonstrated the functional groups, material nature, thermal stability, surface structure, porosity, elemental percentages, ion transportation etc. The electrochemical properties have been studied by TMS theoretical approach which easily determined the important parameters of membranes like transport number, mobility ratio, charge density, charge effectiveness etc. The observed ionic potential and graphical fixed-charge density of both the membranes follows KCl < NaCl < LiCl and KCl > NaCl > LiCl order respectively.