Li4Ti5O12 nanorods have been successfully synthesized via hydrothermal method using TiO2–B as titanium source and template. Such Li4Ti5O12 nanorods with sizes of 100–200 nm in diameter and 1–2 μm in length can be observed. The Li4Ti5O12 nanorods exhibit high discharge capacity of about 101.1 mAh g−1 after 1000 cycles at 20C for the lithium ion battery anode. The Li4Ti5O12 nanorods also show excellent sodium storage performance, which have a reversible capacity of approximately 131.6 mAh g−1 after 100 cycles at 0.1C. Based on the electrochemical performance, it is suggested that Li4Ti5O12 nanorods have a great potential for lithium and sodium ion battery that are available as large-scale storage devices for applications such as automotive and stationary energy storage.