Cr, N-codoped TiO2 mesoporous microspheres have been successfully synthesized by a facile hydrothermal reaction followed by annealing under an ammonia atmosphere. Through introduction of Cr, the nitrogen doping level was increased from 2.81 at.% for N-doped TiO2 to 5.68 at.% for Cr, N-codoped TiO2, which improves the electrical conductivity of TiO2. When used as an anode for lithium-ion rechargeable batteries, the Cr, N-codoping TiO2 microspheres led to an enhanced performance of 159.6 mA h g−1 at 5 C with a drop of less than 1% after 300 cycles.