Novel supported membranes based on polyvinyl alcohol (PVA) were developed using two strategies: first, by the modification of the PVA network, via so-called bulk modification, with the formation of the selective layer accomplished through the introduction of fullerenol and/or poly(allylamine hydrochloride), and second, by the functionalization of the surface with successive depositions of multilayered films of polyelectrolytes, such as poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) on the PVA surface. The membrane surface modification was characterized by scanning electron microscopy and contact angle measurements. The modified PVA membranes were examined for their dehydration transport properties by the pervaporation of isopropyl alcohol-water (80/20% w/w), which was chosen as a model mixture. Compared with the pristine PVA membrane, the main improvement was a marked increase in permeability. It was found that the surface modification mainly gave rise to a higher permeation flux but with a strong reduction in selectivity. Only the combination of both bulk and surface modifications with PEL could significantly increase the flux with a high water content in the permeate (over 98%). Lastly, it should be noted that this study developed a green procedure to prepare innovative membrane layers for dehydration, making use of only water as a working medium.