Polystyrene/silica core-shell spheres were fabricated using polystyrene as templates by hydrolysis and condensation of tetraethyl orthosilicate through a sol-gel process, in which polystyrene was synthesized by emulsion polymerization. Then, hollow silica spheres were obtained after selective removal of the organic polystyrene core from the polystyrene/silica core-shell spheres by tetrahydrofuran etching. The effect of hollow silica spheres on water vapor permeability, mechanical property, and water uptake of polyacrylate membrane were investigated. The microstructure analysis shows that the mean size and wall thickness of hollow silica spheres are 170 nm and 20 nm, respectively. The silica shells consist of amorphous silica seed assembly with a broad size distribution, which roughen the surfaces of hollow silica spheres greatly. The specific surface area of hollow silica spheres is bigger than that of polystyrene/silica core-shell spheres. Hollow silica spheres can significantly improve water vapor permeability of polyacrylate membrane, but lead to the reduction in mechanical property. (C) 2013 Elsevier Inc. All rights reserved.