TiO2 hollow spheres are fabricated by a sol–gel process using carbon spheres as template. The diameter and the shell thickness of the TiO2 hollow spheres are about 400–600nm and 60–80nm, respectively. The electrochemical properties of the hollow spheres are investigated by galvanostatic cycling and cyclic voltammetry (CV) measurements. The initial discharge capacity reaches 291.2mAhg−1 at a current density of 60mAg−1. The average discharge capacity loss is about 1.72mAhg−1 per cycle from the 2nd to the 40th cycles and the coulombic efficiency is approximately 98% after 40 cycles, indicating excellent cycling stability and reversibility.