Novel TiO2(B)@carbon composite nanowires were simply prepared by a two-step hydrothermal process with subsequent heat treatment in argon. The nanostructures exhibit the unique feature of having TiO2(B) encapsulated inside and an amorphous carbon layer coating the outside. The unique core/shell structure and chemical composition is likely to lead to perfect performance in many applications. In this paper, the results of Li-ion battery testing are presented to demonstrate the superior cyclic performance and rate capability of the TiO2(B)@carbon nanowires. The composite nanowires exhibit a high reversible capacity of 560 mAh g−1 after 100 cycles at the current density of 30 mA g−1, and excellent cycling stability and rate capability (200 mAh g−1 when cycled at the current density of 750 mA g−1), indicating that the composite is a promising anode candidate for Li-ion batteries.