A novel method is developed to synthesis TiO2/carbon nanostructured composites (T/CNC) as high-performance anode materials for Li-ion batteries using resorcinol/formaldehyde (RF) as the carbon source. With assistance of hydrofluoric acid (HF) as a shape-controlling agent, TiO2 nanocubes exposed with (001) active facets can be obtained. The T/CNC sample shows higher BET surface area (358 m2 g−1) than the previous materials reported before. When evaluated for lithium storage properties, the T/CNC is able to deliver a capacity of 340.4 mA h g−1 after 90 cycles at 0.59 C, which is superior to those reported in previous work. At a high rate of 15 C, a high reversible discharge capacity of 126.7 mA h g−1 is obtained up to 500 cycles and demonstrates excellent rate performance and long-term cycling stability.