The nanotubes of mixed TiO2(B) and anatase phases, obtained by hydrothermal synthesis and subsequent calcination, are modified with NiO nanoparticles. In the modified products, NiO nanoparticles with poor crystallinity exist inside titania tubes and are attached to the outside surface of the nanotubes according to X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray spectra (EDS) analysis. The titania nanotubes, modified with 5wt.% NiO in which NiO nanoparticles were distributed homogenously, exhibit the optimal cycle performance and a good capability for high rate discharge. The lithium ion diffusion is mainly related to the anatase phase, while the electrochemical reaction activity is attributed to the TiO2(B) phase. Relative to titania nanotubes, NiO-modified nanotubes have a better electrochemical reaction activity, which is beneficial for the improvement of the high rate charge–discharge capability.