A micelle of poly{styrene-b-[3-(methacryloylamino)propyl]trimethylammonium chloride-b-ethylene oxide} with core-shell-corona architecture in aqueous solutions has been successfully applied to the synthesis of hollow silica nanospheres as a new template. Tetramethoxysilane, phenyltrimethoxysilane, and their mixtures were used as silica precursors and the ratio of the precursor to the template influences the shell thickness of the obtained hollow silica.