Nanosized hollow silica spheres with holes in the wall (denoted as silica nanobottles) have been successfully prepared by assembly of functional polymer nanospheres with tetraethoxysilane (TEOS) through hydrothermal methods, coupled with removal of the core by programmed calcination. The functional polymer nanospheres were obtained by emulsifier-free emulsion copolymerization of styrene and (ar-vinylbenzyl) trimethylammoium chloride. The silica nanobottle sample was characterized by thermogravimetric analysis (TG), differential thermal analysis (DTA), transmission electron microscopy (TEM), and nitrogen adsorption techniques. The above characterizations confirm that the silica nanobottles have holes of about 8 nm in the wall and this unique structural feature might be useful for their encapsulation. Furthermore, characterization by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and UV-visible absorption (UV-vis) showed that the luminescent material Eu(TTA)(3)(TPPO)(2) could be effectively encapsulated in silica nanobottles. This reveals that silica nanobottles have potential applications for nanotechniques.