Li₄Ti₅O₁₂ hollow mesoporous microspheres (HMMs) assembled from nanoparticles were successfully synthesized by a facile hydrothermal method and subsequent calcination. They exhibit superior rate capabilities with reversible capacities of 176, 125 and 86 mA h g⁻¹ after 10 cycles at 0.1 C, 20 C and 40 C (7000 mA g⁻¹), respectively. The Li₄Ti₅O₁₂ HMMs also possess outstanding cycle performance with only 3% capacity degradation at 10 C after 500 cycles, which is equivalent to a fade of merely 0.006% per cycle. The comparison with other studies shows that the Li₄Ti₅O₁₂ HMMs possess more promising reversible capacity and rate capability among the values reported for Li₄Ti₅O₁₂. These excellent electrochemical properties may be attributed to the unique HMM structures.