Using poly(vinyl alcohol) (PVA) as coating material, tartaric acid (Tac) and maleic anhydride (Mac) as cross-linking agents and the poly(acrylonitrile) (PAN) hollow fiber ultrafiltration membrane as support layer, the PVA/PAN composite membrane was prepared by dip-coating method used for pervaporation (PV) dehydration of ethyl acetate (EAc)/H2O solution. The PVA/PAN composite membrane was characterized by FT-IR spectra and SEM. The effects of cross-linking agents on the swelling degree and PV performance of PVA/PAN membrane were investigated, respectively. The separation factor of PVA/PAN composite membrane increased while the permeation flux decreased with increasing the contents of cross-linking agents, and PVA/PAN membrane exhibited better PV performance when Tac/PVA mass ratio was 0.2. Furthermore, the PV performance of PVA/PAN composite membrane for EAc/H2O solution was investigated with respect to the feed temperatures and feed water concentrations. For PVA/PAN composite membrane with Tac/PVA mass ratio of 0.2, its performance for 2 wt.% water of EAc solution at 40 degrees C was evaluated as follows: the separation factor and permeation flux were 7270 and 34.5 g m(-2) h(-1), respectively. In addition, PVA/PAN composite membrane was also used for PV dehydration of EAc/ethanol (EtOH)/H2O ternary solution. (C) 2011 Elsevier B.V. All rights reserved.