Here we report a facile approach to synthesize pure nano-Li4Ti5O12 by a glycerol assisted hydrothermal process and subsequent thermal treatment. During the hydrothermal process, the introduction of glycerol helps to control the morphologies of products and significantly improve the electrochemical performance of Li4Ti5O12 as an anode material. On the other hand, an accurate Ti:Li ratio is controlled in order to obtain pure Li4Ti5O12 since the Ti:Li ratio of starting materials sensitively impacts the final composition of product. X-ray diffraction, thermogravimetric-differential scanning calorimetry, field-emission scanning electron microscopy and transmission electron microscopy are used to characterize their structures and morphologies. The glycerol assisted sample annealed at 500 °C can retain a discharge capacity of 154 mAh g−1 after 500 cycles at 5 C and deliver a high discharge capacity of 155 mAh g−1 at 20 C. The excellent cycling and rate performance can be attributed to the minor particle size, lower charge-transfer resistance (15.8 Ω) and larger lithium ion diffusion coefficient (4.32 × 10−11 cm2 s−1).