Zr4+ and F– co-doped TiO2 with the formula of Ti0.97Zr0.03O1.98F0.02 was facilely synthesized by a sol-gel template route. The crystal structure, morphology, composition, surface area, and conductivity were characterized by Raman spectroscopy, energy-dispersive X-ray analysis, scanning electron microscopy, Brunauer?Emmett?Teller measurements, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. The results demonstrate that Zr4+ and F– homogeneously incorporated into TiO2, forming solid solution with an anatase structure. Ti0.97Zr0.03O1.98F0.02 shows outstanding electrochemical properties as Li-ion battery anode in comparison with Ti0.97Zr0.03O2. In particular, upon 35-fold cycling at 1C-rate Zr4+/F– co-doped TiO2 delivers a reversible capacity of 163 mAh g–1, whereas Zr4+-doped TiO2 gives only 34 mA h g–1. Additionally, Zr4+/F– co-doped TiO2 retains a capacity of 138 mA h g–1 during cycling even at 10 C. The enhance performance originates from improved conductivity of Zr4+/F– co-doped TiO2 material through generation of Ti3+ (serving as electron donors) into the crystal lattice and, possibly, due to F-doping blocked the anode surface from attack of HF formed as electrolyte decomposition product.