A novel synthesis containing microwave-assisted HCl etching reaction and precipitating reaction is employed to prepare hierarchical hollow SnO2@TiO2 nanocapsules for anode materials of Li-ion batteries. The intrinsic hollow nanostructure can shorten the lengths for both ionic and electronic transport, enlarge the electrode surface areas, and improving accommodation of the anode volume change during Li insertion/extraction cycling. The hybrid multi-elements in this material allow the volume change to take place in a stepwise manner during electrochemical cycling. In particular, the coating of TiO2 onto SnO2 can enhance the electronic conductivity of hollow SnO2 electrode. As a result, the as-prepared SnO2@TiO2 nanocapsule electrode exhibits a stably reversible capacity of 770 mA hg(-1) at 1 C, and the capacity retention can keep over 96.1% after 200 cycles even at high current rates. This approach may shed light on a new avenue for the fast synthesis of hierarchical hollow nanocapsule functional materials for energy storage, catalyst and other new applications.