Polymeric membranes composed of sodium alginate and polystyrene sulfonic acid-co-maleic acid were prepared using a solution technique. The resulting membranes were characterized by Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Membranes were tested for their ability to separate waterdioxan mixtures in the temperature range of 30-50 degrees C. The experimental results demonstrated that both flux and separation factor were increased simultaneously with increasing the PSSA-MA content in the membrane. The permeation flux of pure Na-Alg membrane was increased dramatically from 7.1 to 10.6 x 10(-2) kg/m(2)h with increasing the mass% of PSSA-MA, and correspondingly its separation factor was increased from 6400 to 22,500 at 30 degrees C for 10 mass% of water in the feed. The total flux and flux of water were found to be overlapping each other particularly for crosslinked membranes, suggesting that these membranes could be used effectively to break the azeotropic point of waterdioxan mixture. From the temperature dependent permeation values, the Arrhenius activation parameters were estimated. (c) 2013 Elsevier Ltd. All rights reserved.