Poly(vinyl alcohol) (PVA) fibrous mats dealt with polyoxometalate containing vanadium were prepared by electrospirming method. The fibrous mats were characterized by infrared spectra, X-ray powder diffraction patterns, and scanning electron microscopy photographs. The results showed that PVA could combine with polyoxometalate by intermolecular H-bonding. The studies of the diameter distributions indicated that the average diameter of the fibrous mats was about 260-420 nm. The effects of the polyoxometalate content, electrode potential, temperature, and time on the swelling capacity of the fibrous mats in water were investigated. The existence of the polyoxometalate containing vanadium was advantaged for the crosslinking of PVA fibrous mats. The swelling degree of PVA fibrous mats containing polyoxometalate dealt with 383 K for 18 h approached zero in water. (C) 2007 Wiley Periodicals, Inc.