Electrochemical properties of TiO2 hollow microspheres from a green and template-free route were investigated by charge–discharge, cyclic voltammograms, cycle performance, and high rate capacities measurements. The storage capacity of Li ions in the first discharge process was 290.3mAhg−1. During the successive 10 cycles, the reversible capacity stayed in the range from 290 to 130mAhg−1 with a capacity fading of 8.96% per cycle. Cyclic voltammograms measurement exhibited only a pair of reduction/oxidation peaks, indicating TiO2 hollow microspheres with a good crystalline quality was approached in this route.