A facile method to prepare SnO2 hollow micro spheres has been developed by using SiO2 microspheres as template and Na2SnO3 as tin resource. The obtained SnO2 hollow microspheres were characterized by X-ray diffraction, scanning electron microscopy, high resolution and transmission electron microscopy, and Brunauer Emmett Teller analysis, and their sensing performance was also investigated. It was found that the diameter of SnO2 hollow microspheres can be easily controlled in the range of 200-700 mm, and the shell thickness can be tuned from 7.65 to 30.33 nm. The sensing tests showed that SnO2 hollow microspheres not only have high sensing response and excellent selectivity to acetone, but also exhibit low operating temperature and rapid response and recovery due to the small crystal size and thin shell structure of the hollow microspheres, which facilitate the adsorption, diffusion, and reaction of gases on the surface of SnO2 nanoparticles. Therefore, the SnO2 hollow microsphere is a promising material for the preparation of high-performance gas sensors.