Poly(vinyl alcohol) (PVA) fiber aggregates contained 20 and 80 wt.% H3PW12O40 were prepared by an electrospinning method. The fiber aggregates were characterized by IR, XRD and scanning electron microscope (SEM) photographs. The results indicated that PVA could combine with H3PW12O40 by intermolecular H-bonding. The studies of the diameter distributions indicated that the average diameter of the fibers was 370 and 520 nm for 20 and 80 wt.% H3PW12O40, respectively. The Brunauer-Emmett-Teller (BET) surface area increased with decreasing the average diameter of the fibers. Swelling behavior of the fiber aggregates in water was investigated. The existence of H3PW12O40 was advantaged for the crosslinking of PVA. (C) 2004 Elsevier B.V. All rights reserved.