In the present work, hierarchically structural TiO2 nanorods composed of rutile core and anatase shell were successfully synthesized via a one-step hydrothermal route for the first time, and then were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning and transmission electron microscopy (SEM/TEM) measurements. It was found that the crystal phases of the same can be easily adjusted by changing the amount of the reactant during the reaction process. Furthermore, the sample was used as an anode for lithium-ion intercalation and exhibited high capacity and long-term cycling stability due to the synergistic effects of dual-phase TiO2. For instance, the capacities of 102.7 and 84.7mAhg−1 can be kept at 10 C for 1000cycles and 20 C for 5000cycles, respectively.