In the present study, crosslinked poly(vinyl alcohol) (PVA) membranes were prepared using poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) at different crosslinking temperatures. The crosslinked PVA membranes were prepared by varying the content of PSSA-MA (5-11 wt%). The PSSA-MA was used both as a crosslinking agent and as a donor of the hydrophilic group (-SO3H and/or -COOH). The crosslinked PVA/PSSA_MA membranes were characterized using FT-IR spectroscopy, thermogravimetric analysis (TGA) and investigated in relation to proton conductivity and methanol permeability. The proton and methanol transport decreased with increasing the PSSA-MA content. The effect of crosslinking may be more dominant than that of the increase of the number of ionic exchange sites in this system. The proton conductivities and the methanol penneabilities of all the membranes were in the range of 10(-3) to 10(-2) S/cm and 10(-7) to 10(-6) cm(2)/S, respectively, in the temperature range of 25-90 degrees C, depending on the crosslinking conditions. (c) 2006 Elsevier B.V. All rights reserved.