Periodic ordered Nafion-silica-heteropolyacids electrolyte is synthesized through a facile multiphase self-assembly between the positively charged silica, negatively charged HPW acids (H3PW12O40) and Nafion ionomers. The results exhibit uniform nanoarrays with longrange order of the electrolyte. The well-ordered proton conducting sites make the proton move through the membrane freely with low humidity dependence of proton transportation through the electrolyte. The Nafion-Silica-HPW electrolyte displays desirable conductivity at both low and elevated temperature. The proton conductivity of Nafion-Silica-HPW electrolyte at absolutely dry condition of 200 degrees C is 0.044 Scm(-1). At low temperature of 75 degrees C, the proton conductivities of the electrolyte were 0.029 Scm(-1) and 0.093 Scm(-1) at absolute dry (0 RH%) and full humidifying condition (100 RH%), respectively. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.