In this work, the polyethylene glycol (PEG) hybrid materials composited with substituted germanic heteropoly acids were prepared. Infrared (IR) spectra revealed that the Keggin structure characteristic of the GeM11VO405-, anion were present in the hybrid materials. At room temperature (20 degrees C), the conductivity of the products is 4.07 X 10(-3) S cm(-1) and 2.12 X 10(-3) S cm(-1), respectively. The results indicated that the conductivity of substituted germanic heteropoly acids PEG hybrid materials is higher than that of the corresponding pure substituted germanic heteropoly acids. According to the experimental results, we proposed a possible mechanism of the proton conduction of the hybrid materials. (c) 2007 Wiley Periodicals, Inc.