In this work, the polyvinyl alcohol (PVA) films composited with molybdotungstovanadogermanic heteropoly acid were prepared. Infrared spectra (IR) revealed that the Keggin structure characteristic of the GeMo2W9VO405- anion was present in PVA films. At room temperature (20 degreesC), the conductivity of the samples of different HPA content increased from 2.46 x 10(-3) to 9.92 x 10(-3) S cm(-1). The results indicated that they are new kind of excellent high-proton conductor. (C) 2004 Elsevier B.V. All rights reserved.