To develop of novel green high-performance blend membranes for enchanced pervaporation dehydration, biopolymers sodium alginate (SA) and hydroxyethyl cellulose (HEC) were chosen as a membrane material. Several approaches were used for the preparation of membranes with improved properties: (1) the selection of the optimal biopolymer ratio in the matrix, (2) bulk modification by the introduction of fullerenol in blend matrix, (3) the selection of the optimal cross-linking agent, and (4) surface modification by layer-by-layer technique for the deposition of polyelectrolytes. Structure of the developed membranes were investigated by spectroscopic (FTIR and NMR) and microscopic (SEM and AFM) methods. The physicochemical properties were studied by TGA, contact angle and swelling degree measurements. Transport properties of developed HEC/SA membranes were tested in pervaporation dehydration of isopropanol in a wide concentration range. It was demonstrated that the combination of several strategies (bulk and surface modifications) resulted to changes in membrane structure causing improved performance of the membrane.