For the first time, poly(vinyl alcohol) (PVA)/H4SiW12O40 ultra-fine fiber mats (80 wt% H4SiW12O40) was prepared by electrospinning technique. Calcining the PVA/HPA fiber mats at 380 degreesC for 4 h got pure H4SiW12O40 ultra-fine fiber mats. (C) 2003 Elsevier Science B.V. All rights reserved.