Novel Ni-doped titanate derived from protonated layered titanate has been fabricated via a simple ion-exchange process at room temperature. The as-synthesized product was calcined at 400 °C for 3 h to obtain the Ni–TiO2 (anatase). The crystal structure of Ni–TiO2 was studied by X-ray diffraction (XRD) and the surface chemistry was studied by X-ray photoelectron spectroscopy (XPS). It was found that doped nickel ions had inhibition effects on the crystallization of TiO2 during calcination. The electrochemical properties of Ni–TiO2 and undoped TiO2 were both tested as anode materials for lithium-ion batteries at room temperature. While the undoped sample exhibited a mediocre performance, having a discharge capacity of 132 mAhg−1 after 50 cycles, the nickel-ion doped sample demonstrated noticeable improvement in both of its discharge capacity and rate capability; with a high capacity value of 226 mAhg−1 after 50 cycles. This improvement of lithium ion storage capability of Ni–TiO2 can be ascribed to the Ni-doping effect on crystallinity and the modification of electrode/electrolyte interface of the TiO2 structure.