Novel sandwich-like TiO2@C composite hollow spheres with {001} facets exposed are obtained through hydrothermal carbon-coating treatment for the first time. Based on investigations by transmission electron microscopy (TEM), scanning electron microscopy (FESEM), XRD, laser Raman spectra, and N-2 adsorption-desorption isotherms, TiO2 shells are proved to be wrapped in porous carbon layers, which provide conductive support for TiO2, resulting the improvement in electronic conductivity and diffusion of Li+ Moreover, these TiO2 shells expose the reactive {001} facets, which facilitate Li+ insertion/extraction. Through combining the above advantages, TiO2@C composite hollow spheres show more superior rate capability and higher stability than TiO2 nanoparticles (Degussa P25), TiO2 nanosheets with {001} facets exposed, and TiO2 hollow spheres before carbon-coating. This method may be extended to synthesize other sandwich-like composite hollow spheres for energy storage. (C) 2012 Elsevier B.V. All rights reserved.