Dual-phase Li4Ti5O12–TiO2 nanocrystallines are prepared by a hydrothermal process and subsequent heat treatment. The as-prepared Li4Ti5O12–TiO2 nanocrystallines measure around 15–25nm in size and have abundant phase interfaces. Electrochemical measurements demonstrate that dual-phase Li4Ti5O12–TiO2 exhibit good electrochemical performance over individual single-phase Li4Ti5O12, especially at high current rates. Initial discharge capacities of dual-phase Li4Ti5O12–TiO2 nanocrystallines are 241 and 202mAhg−1 at discharge rates of 0.2 and 5C, respectively. Even after 50 cycles at 20C, the capacity still remains 140mAhg−1, which is four times greater than that of single-phase Li4Ti5O12 (29mAhg−1). The high electrochemical performance indicates that dual-phase Li4Ti5O12–TiO2 nanocrystallines are highly promising anode materials for lithium ion battery applications.