Novel polyelectrolyte complexes (PECs) based on dual anionic group copolymers were prepared and their homogeneous membranes were subjected to pervaporation dehydration of acidic feed. Dual anionic copolymers containing weakly charged acid groups (COO-) and strongly charged acid groups (SO3-), poly(sodium acrylate-co-sodium sytyrenesulfonate) (P(AANa-co-SSNa)), with different compositions were synthesized by radical solution polymerization. SPECs (PECs containing SO3 groups) consisted of negatively charged P(AANa-co-SSNa) and positively charged chitosan (CS) and their homogeneous SPEC membranes (SPECMs) with tunable compositions were prepared. Fourier transform infrared spectroscopy (FT-IR) and X-ray photo electron spectroscopy (XPS) were used to characterize the structure and composition of P(AANa-co-SSNa) and its SPECs. Field emission scanning electron microscopy (FESEM) and contact angle (CA) were used to survey surface properties of SPECMs. Effects of pH values and temperatures of feed mixtures on the swelling behavior and pervaporation dehydration performance of SPECMs were examined. It is found that SPECMs containing SO3 groups are resistant of acidic feed and display very good pervaporation performance even for the low pH feed. For instance, the water concentration in permeate for SPECM - 0.30 reaches as high as 99.4 wt%, which is much higher than 60 wt% for PECM for water-isopropanol mixture with pH 1.2, and also maintains operation stability. The SPECMs could find considerable potential application to pervaporation dehydration of acidic feed. (c) 2012 Elsevier B.V. All rights reserved.