Hollow silica spheres have been successfully fabricated by means of a miniemulsion technique, in which miniemulsion droplets of tetraethoxysilane (TEOS) and octane were prepared with cetyltrimethylammonium bromide as a surfactant and hexadecane as a costabilizer and used as templates. As the TEOS diffused out from the droplets, it was hydrolyzed and condensed to form a silica shell at the oil/water interface. In this way, hollow silica spheres could be obtained directly since the miniemulsion droplets of octane could be evaporated very easily during the reaction process or the drying process; neither an additional dissolution nor a calcination process or additional surface modification of the templates were needed.