Sodium alginate (SA) and chitosan (CS) blended membranes were crosslinked with maleic anhydride (MA) for the separation of 1,4-dioxane/water mixtures at 30 degrees C by pervaporation (PV). The membranes were characterized by Fourier transform infrared (FTIR) analysis and Ion Exchange Capacity (IEC) to verify the crosslinking. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) pattern were used to observe the thermal degradation and crystalline nature of the membrane respectively. The membrane performance was studied by calculating flux, selectivity, and pervaporation separation index. Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the membranes in pure liquids as well as in binary mixtures. The effects of experimental parameters such as feed composition, membrane thickness, and permeate pressure on separation performance of the crosslinked membranes were determined. The experimental result suggested that the membrane has a good potential for breaking the aqueous azeotrope 1,4-dioxane.