Developing a facile and green methodology to prepare nanostructured transition metal oxides (TMD) formed by sub-10 nm nanocrystals for the electrochemical energy conversion and storage remains an important challenge. Herein, we present hollow TiO2 submicrospheres, assembled by 10 nm units via a facile one-step, low-temperature hydrothermal strategy. When used as anodes for lithium ion batteries, the submicrospheres could exhibit excellent rate capabilities of 223, 153, 44 and 22 mA h g−1 at 1C, 10C, 100C and 300C, respectively. More importantly, they demonstrated a long-term cycling performance and structural stability over 2000 cycles at 10C and even 300C. The superb performances mainly originate from the integration of distinct advantages of the well-defined hollow structures and tiny TiO2 grains into a single component via the environmental friendly synthesis strategy.