The hollow BaWO 4 nanospheres were successfully synthesized by using polymer PVP micelle as templates at room temperature. The products were characterized by the techniques of X-ray diffraction (XRD) and transmission electron microscopy (TEM). A growth mechanism of the hollow BaWO 4 nanospheres was proposed. The luminescence properties were investigated and the prepared structures displayed a very strong blue luminescence at the room temperature. Based on these properties, the hollow BaWO 4 nanospheres may have promising for applications in the fabrication of photoelectric materials.