We have developed a simple one-step template-free method for the controlled synthesis of hollow or hollow core/shell-type SnO₂ nanostructures with controllable sizes in the range of 200 – 500 nm. This method is based on hydrothermal treatment of stannate in a mixed ethanol-water solvent. An inside-out Ostwald ripening mechanism is proposed to account for the template-free formation of these hollow nanostructures. A shortcoming of the method is that size uniformity of the as-synthesized SnO₂ hollow nanoparticles is difficult to achieve. To solve this problem, the hydrothermal method has been extended to synthesize SnO₂ hollow nanostructures with controlled sizes using monodisperse silica nanospheres as templates. Remarkably, uniform surface coating can be achieved without any prior surface modification. By repeated hydrothermal deposition or controlling the synthetic conditions, multi-shelled structures can also be prepared. These hollow SnO₂ nanostructures may find applications in many important technological fields. Here we study their application as electrodes for lithium ion batteries and report encouraging initial results. We have also designed new nanostructured SnO₂/carbon composite anode materials with hollow spherical structure. 3D carbon networks or shells in nanoscale can be effectively integrated with the SnO₂ shells by selective infiltration of carbon precursor in solution followed by carbonization. The carbon networks act as both physical buffering cushion for the intrinsic large volume change and electrical conducting path. As a result, the capacity retention of the composite electrode is largely improved.