Core–shell Li4Ti5O12@CeO2 nanosphere has been synthesized by a one-pot co-precipitation method. The structure and morphology of the as-prepared materials have been analyzed by X-ray diffraction and transmission electron microscopy. The results show that CeO2 is successfully coated on the surface of the Li4Ti5O12 besides partial doping of Ce4+ into the Li4Ti5O12 structure. The Li4Ti5O12@CeO2 nanosphere exhibits excellent capacity of 152 mAh g−1 even after 180 cycles at 10 C, with no noticeable capacity fading. Furthermore, the sample shows much improved rate capability at 40 C compared with pure Li4Ti5O12 when used as anode material for lithium-ion batteries. The introduction of CeO2 enhances not only the electric conductivity of Li4Ti5O12, but also the lithium ion diffusivity in Li4Ti5O12, resulting in significantly improved electrochemical performance of the Li4Ti5O12.