Using Na+ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA-PVA/PSf hollow fiber composite membrane was fabricated by dip-coating method. The membranes were post-treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H2SO4 as a catalyst. PFSA-PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H2O mixture. Based on the experimental results, PFSA-PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H2O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA-PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post-treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post-treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post-treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA-PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160 degrees C for 1 h, then chemical crosslinking at 40 degrees C for 3 h in 4% MAC aqueous solution. (c) 2007 Wiley Periodicals, Inc.