A novel layer-by-layer approach has been developed to synthesize polycrystalline SnO2 hollow spheres with tunable shell thickness and size using SiO2 spheres as a template. The surface of the SiO2 spheres has been first modified by the polyelectrolyte, and subsequently, the compact SnO2 layer has deposited on the surface of the SiO2 spheres through a redox reaction because of the electrostatic attraction between the charged species. After HF etching treatment, the uniform SnO2 hollow spheres have been obtained. The approach presented herein has been extended to synthesize other metal oxide and sulfide hollow spheres such as In2O3 and ZnS. Moreover, the as-synthesized SnO2 hollow spheres have been applied in lithium-ion battery and show improved performance compared with SnO2 nanoparticles. The high surface area and stable hollow structure of the SnO2 hollow spheres may be responsible for the improved performance.