Abstract TiO 2 hollow microspheres with the shell consisting of nanotubes have been successfully synthesized via a template-free hydrothermal process and subsequent treatments. The electrochemical properties of the anatase sample have been investigated by cyclic voltammetry and galvanostatic method. The initial Li insertion/extraction capacity at a current density of 0.2 C reach 290 and 232 mAh g −1 respectively. Moreover, as-prepared TiO 2 delivers a reversible capacity of ca. 150 mAh g −1 after 500 cycles at 1 C, and it also shows superior high rate performance (e.g., 90 mAh g −1 at 8 C) without any modification.