TiO2 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 0.2C reach 290 and 232mAhg−1 respectively. Moreover, as-prepared TiO2 delivers a reversible capacity of ca. 150mAhg−1 after 500 cycles at 1C, and it also shows superior high rate performance (e.g., 90mAhg−1 at 8C) without any modification.