In the present work, the novel dense and supported membranes based on polyvinyl alcohol (PVA) with improved transport properties were developed by bulk and surface modifications. Bulk modification included the blending of PVA with chitosan (CS) and the creation of a mixed-matrix membrane by introduction of fullerenol. This significantly altered the internal structure of PVA membrane, which led to an increase in permeability with high selectivity to water. Surface modification of the developed modified dense membranes, based on composites PVA-CS and PVA-fullerenol-CS, was performed through (i) making of a supported membrane with a thin selective composite layer and (ii) applying of the layer-by-layer assembly (LbL) method for coating of nano-sized polyelectrolyte (PEL) layers to increase the membrane productivity. The nature of polyelectrolyte type-(poly(allylamine hydrochloride) (PAH), poly(sodium 4-styrenesulfonate) (PSS), poly(acrylic acid) (PAA), CS), and number of PEL bilayers (2-10)-were studied. The structure of the composite membranes was investigated by FTIR, X-ray diffraction, and SEM. Transport properties were studied during the pervaporation separation of 80% isopropanol-20% water mixture. It was shown that supported membrane consisting of hybrid layer of PVA-fullerenol (5%)-chitosan (20%) with five polyelectrolyte bilayers (PSS, CS) deposited on it had the best transport properties.