Homogeneous TiO₂@C composite nanospheres are synthesized by a direct pyrolysis strategy using Ti-containing organic–inorganic polymers as precursors. The TiO₂@C composite nanospheres possess uniform distribution of tiny TiO₂ nanoparticles confined in the carbon matrix with a homogeneous structure. The carbon phase can not only improve the conductivity but also prevent the aggregation of TiO₂ nanoparticles. When evaluated as anodes for lithium-ion batteries, the TiO₂@C nanocomposites demonstrate a high reversible specific capacity of 207 mA h g⁻¹ at 0.5 C (1 C = 250 mA g⁻¹) after 50 cycles and a stable cycling performance in comparison to pure TiO₂ nanospheres. This work offers a new pathway for realization of carbon-based composite materials for use as high performance anodes in LIBs.