We demonstrate the hollow triple-shelled SiO2/TiO2/polypyrrole (Ppy) nanospheres (NSs), which are readily synthesized through the hard templating method and sequential vapor deposition polymerization (VDP), for application in lithium ion battery (LIB) anodes. The resultant NSs with a hetero-composition show a uniform hollow spherical nanomorphology consisting of SiO2, TiO2, and Ppy layers, as verified by the Si, Ti, C, and 0 signals of the STEM images. The hollow SiO2/TiO2/Ppy NSs have about a threefold higher capacity of 433 mA h/g compared to 147 mA h/g of TiO2 at a specific current of 44 mA/g, which is close to the theoretical value of TiO2. In particular, the hollow triple-shelled NSs exhibit good rate (76% capacitance retention in the range of 44-440 mA/g) and cyclic (98% in the fifty cycles) performances due to the reversible redox reaction occurring on the Ppy outer shell. The enhanced performance of the SiO2/TiO2/Ppy NSs is attributed to the synergistic effect of the OD nanostructure and hetero-composition. (C) 2013 Elsevier B.V. All rights reserved.