Several blend membranes were prepared from different weight ratios of polyvinyl alcohol (PVA) and hydroxyethyl cellulose (HEC) and these unfilled membranes were crosslinked with maleic acid. In a similar way mixed matrix blend membranes were also prepared by varying weight ratio of PVA and HEC with micro and nano bentonite filler in each of these blends. These membranes were used for pervaporative dehydration of 89wt% tetrahydrofuran (THF). Three membranes designated as UF (unfilled), MF2 (containing 2wt% micro filler) and NF2 (containing 2wt% nano filler) showing the best results for flux and selectivity were identified. These membranes were characterized by FTIR, UV, XRD and DTA-TG and used for separation of 80–99wt% THF from water by pervaporation. The NF2 membrane was found to show the best results in terms of flux and separation factor.