Novel mixed matrix dense and supported membranes based on biopolymer sodium alginate (SA) modified by fullerenol were developed. Two kinds of SA-fullerenol membranes were investigated: untreated and cross-linked by immersing the dry membranes in 1.25 wt % calcium chloride (CaCl2) in water for 10 min. The structural and physicochemical characteristics features of the SA-fullerenol composite were investigated by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopic methods, scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA), and swelling experiments. Transport properties were evaluated in pervaporation dehydration of isopropanol in a wide concentration range. It was found that the developed supported cross-linked SA-5/PANCaCl2#nbsp;membrane (modified by 5 wt % fullerenol) possessed the best transport properties (the highest permeation fluxes 0.64-2.9 kg/(m2#nbsp;h) and separation factors 26-73,326) for the pervaporation separation of the water-isopropanol mixture in the wide concentration range (12-90 wt % water) at 22 °C and is suitable for the promising application in industry.