The polyvinyl chloride (PVC) based carboxymethyl cellulose Ce(IV) molybdophosphate composite membrane are prepared and characterized by the Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR), and thermogravimetric analysis (TGA) studies. The inorganic–organic composite membrane was found to be crystalline in nature with consistent arrangement of particles and indicating no sign of visible cracks. The FTIR spectra verify the binding of organic polymer with inorganic component. The membrane was found to be cation-selective. The order of surface charge density for uni-univalent electrolytes solution was found to be KCl > NaCl > LiCl.