Soluble polyelectrolyte complexes (PECs) between chitosan (CS) and sodium carboxymethyl cellulose (CMCNa) were synthesized in aqueous hydrochloric acid (HCl) and obtained in their solid form. FT-IR, elemental analysis (EA), thermal gravity analysis (TGA), wide-angle X-ray diffraction (WAXD), and viscometry were used to characterize the chemical structure, composition, thermal stability, crystallinity and solution property of PECs, respectively. These PECs could be dissolved in aqueous NaOH and their homogeneous polyelectrolyte complex membranes (HPECMs) were made by solution casting method. Both the surface morphology of HPECMs and the morphology of single PEC aggregate were examined by field emission scanning electron microscope (FESEM), and atomic force microscopy (AFM). Effects of the water content in aqueous ethanol and temperature on the swelling behavior and pervaporation dehydration of HPECM were examined. A good performance of J = 1.14 kg/m(2) h, alpha = 1062 was obtained with HPECM0.25 in dehydrating 10 wt.% water-ethanol at 70 degrees C. The swelling behavior and pervaporation performance were interpreted in terms Of Structure characteristics of both PECs and HPECMs. (C) 2009 Elsevier B.V. All rights reserved.