Thiol-functionalized mesoporous poly (vinyl alcohol)/SiO2 composite nanofiber membranes and pure PVA nanofiber membranes were synthesized by electrospinning. The results of Fourier transform infrared (FTIR) indicated that the PVA/SiO2 composite nanofibers were functionalized by mercapto groups via the hydrolysis polycondensation. The surface areas of the PVA/SiO2 composite nanofiber membranes were >290 m(2)/g. The surface areas, pore diameters and pore volumes of PVA/SiO2 composite nanofibers decreased as the PVA content increased. The adsorption capacities of the thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes were greater than the pure PVA nanofiber membranes. The largest adsorption capacity was 489.12 mg/g at 303 K. The mesoporous PVA/SiO2 composite nanofiber membranes exhibited higher Cu2+ ion adsorption capacity than other reported nanofiber membranes. Furthermore, the adsorption capacity of the PVA/SiO2 composite nanofiber membranes was maintained through six recycling processes. Consequently, these membranes can be promising materials for removing, and recovering, heavy metal ions in water. Crown Copyright (C) 2010 Published by Elsevier Ltd. All rights reserved.