Spinel nano-sized Li4Ti5O12 anode material of secondary lithium-ion battery has been successfully prepared by solid state reaction using axiolitic TiO2 assembled by 10–20nm nanoparticles and Li2CO3 as precursors. The synthesis condition, grain size effect and corresponding electrochemical performance of the special Li4Ti5O12 have been studied in comparison with those of the normal Li4Ti5O12 originated from commercial TiO2. We also propose the mechanism that using the nano-scaled TiO2 with special structure and unexcess Li2CO3 as precursors can synthesize pure phase nano-sized Li4Ti5O12 at 800°C through solid state reaction. The prepared nano-sized Li4Ti5O12 anode material for Li-ion batteries shows excellent capacity performance with rate capacity of 174.2, 164.0, 157.4, 146.4 and 129.6mAhg−1 at 0.5, 1, 2, 5 and 10C, respectively, and capacity retention of 95.1% after 100 cycles at 1C. In addition, the specific capacity fade for the cell with the different Li4Ti5O12 active materials resulted from the increase of internal resistance after 100 cycles is compared.