Nanocrystalline anatase TiO2 is successfully synthesized via a facile and rapid mechanochemical reaction with subsequent annealing in different atmospheres. Transmission electron microscopy observation and X-ray diffraction peak broadening reveal the average crystallite size to be about 11nm. Cyclic voltammetry and galvanostatic discharge–charge tests at various current densities are carried out to explore electrochemical properties of the synthesized materials. The first discharge and charge capacities can reach 325mAhg−1 and 234mAhg−1, respectively. Moreover, nanocrystalline TiO2 also exhibits good rate capability and excellent capacity retention for over 700 cycles.