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In this paper, a one-pot synthesis of WO3 hollow sphere nanostructure has been realized via a one-pot template-free solvothermal method. X-Ray diffraction patterns demonstrated that the products are pure monoclinic WO3. Based on the observation of scanning electronic microscopy (SEM) and transmission electron microscopy (TEM), it was revealed that the as-prepared WO3 nanospheres have a diameter of around 2 mu m and are hollow structures with shell thickness of about 300 nm which are constructed by numerous oriented nanocrystals. Sensors based on the synthesized WO3 hollow nanospheres exhibited high selectivity to NO2 at low operating temperature. The detection limit can be as low as similar to 40 ppb level.