Photoluminescence measurements showed that needle-like tungsten oxide nanostructures synthesized at 590°C to 750°C by the thermal evaporation of WO3 nanopowders without the use of a catalyst had an intense near-ultraviolet (NUV) emission band that was different from that of the tungsten oxide nanostructures obtained in other temperature ranges. The intense NUV emission might be due to the localized states associated with oxygen vacancies and surface states.