A facile hydrothermal approach has been developed to synthesize the nanostructured dual phase Li4Ti5O12/TiO2 composite. The fabrication process simply involves the hydrothermal treatment of tetrabutyl titanate with LiOH in glycerol-water solution and a subsequent calcination procedure. The calcination treatment at 500°C leads to the phase evolution from Li1.81H0.19Ti2O5•nH2O to Li4Ti5O12/TiO2 composite with a particle size of about 30nm. It is found that glycerol as chelating agent plays an important role in the formation of TiO2. The Li4Ti5O12 and anatase TiO2 nano-composite exhibits rich hierarchical pores and a specific surface area of 91.88m2 g−1, delivers ultrahigh rate performance of over 150mA h g−1 at 20C, as well as superior capacity retention of 151.4 mAh g−1 after 100 cycles at 1C. It is therefore concluded that Li4Ti5O12/TiO2 nano-composite is a promising candidate for applications in high rate lithium ion batteries.