Well-defined submicron Li4Ti5O12-Li3xLa(2/3)−xTiO3 (LTO-LLTO) materials have been synthesized by a solid-state reaction followed by hydrothermal procedure. Li4Ti5O12-Li3xLa(2/3)−xTiO3 materials show much improved rate capability and specific capacity compared with pristine Li4Ti5O12 when used as anode materials for lithium-ion batteries. The results here give clear evidence of the utility of Li3xLa(2/3)−xTiO3 (LLTO) to improve the kinetics of Li4Ti5O12 toward fast lithium insertion/extraction. LTO-LLTO (10 wt%) shows a high capacity of 101 mAh g−1 even at a charge-discharge rate of 5 C in the 150th cycle, about 150% that of pristine Li4Ti5O12 particles (68 mAh g−1). The improved high-rate capability, cycling stability, fast charge-discharge performance of LTO-LLTO composites can be ascribed to the improvement of electrochemical reversibility, lithium ion diffusion and ionic conductivity by LLTO modifying.