Using SnSO4, D-glucose, urea and water, hierarchical shell-core SnO2 microspheres were successfully synthesized via a simple hydrothermal method. The characterization results showed that the sizes of as-prepared SnO2 microspheres were 0.6–1μm, with shell thicknesses of 40-60 nm. The shell and large core of the SnO2 microspheres were all comprised of the same basic rice-like nanoparticles with diameters of 16-25 nm and lengths of 16-45 nm. Further investigaton showed that the glucose and urea served as structural guiding agents, and urea facilitated the formation of the hierarchical structure. The as-prepared SnO2 nanomaterials were used to fabricate a gas sensor with an electrode blade used for the gas sensitivity tests. The hierarchical shell-core SnO2 microspheres exhibited high sensitivity and selectivity toward ethanol, with a responsivity of 63.8 for 50 ppm ethanol at 250 ℃, while the response and recovery time were 7 s and 28 s, respectively. Moreover, the responsivity of the materials showed good linearity at ethanol concentrations from 500 ppb to 10 ppm. The simple synthetic method, environmentally-friendly raw materials, and excellent gas sensitivity demonstrate that the as-prepared SnO2 nanomaterial has great potential applications for the sensing of ethanol gas.