Cube-like anatase TiO2 mesocrystals have been fabricated successfully by using amorphous titanate as a precursor. The size and shape of the synthesized mesocrystals are uniform with an average size of 100 nm. Interestingly, the low index facets of (100), (010) and (001) are exposed completely, forming the special cube-like shape. When used as an anode for lithium-ion batteries, anatase TiO2 mesocrystals exhibit an excellent lithium storage ability. A capacity of 166 mA h g−1 can be remained after 800 cycles at 5C, demonstrating a good long-term cycling performance. Furthermore, an average reversible capacity of 148 mA h g−1 can be also maintained even at a rate as high as 20C. Such an excellent electrochemical performance can be attributed to the special cube-like shape of TiO2 mesocrystals with exposed facets, which facilitate lithium-ion diffusion.