In this work biopolymers sodium alginate (SA) and hydroxyethyl cellulose (HEC) were selected for the development of novel green high-performance blend membranes for pervaporation isopropanol dehydration using bulk and surface modifications. Several approaches were applied for the improvement of membrane properties: (1) the selection of the optimal ratio of biopolymers in the matrix, (2) the introduction of carbon nanoparticle - fullerenol in blend matrix, (3) the selection of the optimal cross-linking agent, and (4) the application of layer-by-layer technique for the deposition of various polyelectrolytes on surface of supported membranes. Structure and physicochemical properties of the developed membranes were investigated by various analysis methods (FTIR and NMR spectroscopies, SEM and AFM microscopies, TGA, contact angle and swelling degree measurements). Transport properties of developed HEC/SA-based membranes were evaluated in pervaporation dehydration of isopropanol in a wide range of concentrations. Cross-linked supported HEC/SA/fullerenol (5%) membrane had the optimal transport characteristics in pervaporation dehydration of isopropanol. The surface modification of this membrane with 5 bilayers of polyelectrolytes resulted in the significant increase of permeation flux with lower selectivity. It was demonstrated that the use of the surface or/and bulk modifications led to a significant improvement of the membrane transport characteristics due to significant changes in membrane inner and surface structure.