Vinyl functionalized hollow silica spheres (HSSs) were prepared via a template method and surface modification thereafter. Poly(vinylbenzyl phosphonic acid) (PVBPA) grafted HSSs (HPSSs) were prepared via emulsion polymerization of diisopropyl p-vinylbenzyl phosphonate (DIPVBP) on the surface of HSSs, and hydrolysis thereafter. The chemical structure and morphology of HPSSs were characterized by FTIR and TEM. A series of proton exchange membranes based-on Nafion (R) 212 and HPSSs were prepared via solution casting. The water uptake, swelling ratio, mechanical properties, thermal behavior, proton conductivity, and chemical oxidative stability of the composite membranes were investigated. The addition of HPSSs in Nafion (R) membranes can improve the water retentivity of the composite membranes. The composite membranes with HPSSs exhibit higher water uptake and proton conductivity than that of the recast Nafion (R) membranes. The water uptake and the proton conductivity of the composite membranes increase with increasing HPSSs loading. With the higher water retentivity, the membranes exhibit high proton conductivity at high temperature (1.6 x 10(-1) S cm(-1) at 125 degrees C). (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.