The study reports on the development of hybrid nanocomposite membranes of poly(vinyl alcohol) (PVA) loaded with metal oxide of cerium oxide (CeO2) nanoparticles in different compositions from 1 to 10 wt. % that are used for pervaporation (PV) dehydration of ethanol at azeotropic point from aqueous mixtures i.e. 4.1 wt. % at 30°C. The PV performance of hybrid nanocomposite membranes were much superior to that of pristine PVA membrane in terms of selectivity and flux due to increased hydrophilicity of PVA membrane in the presence of nanoparticles. The membranes were crosslinked with tetraethylortho silicate (TEOS). Morphology of the membranes was assessed by scanning electron microscopy (SEM). It is observed that flux and selectivity increased analytically with increasing amount of nano CeO2 particles in the PVA matrix. In case of hybrid adsorbent membrane containing 10 wt. % CeO2, selectivity for water was 1821 and flux 0.567 kg/cm2 h that was attributed to the combined effects of molecular adhesion between particle surfaces and PVA matrix as well as higher selectivity of the adsorptive membrane as compared to plain PVA membrane.