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Ce-doped Li₄Ti₅O₁₂ anode materials are prepared via a solid state reaction. The Ce is designed to replace of Ti (Li₄Ti_5−xCe_xO₁₂) or take the place of octahedral interstice (Li₄Ti₅Ce_xO₁₂). The structure and morphology of these materials are characterized and their electrochemical performance is investigated. The structure analysis results show that it is difficult for Ce to dope into the lattice of Li₄Ti₅O₁₂, only few Ce can dope in the lattice of Li₄Ti₅O₁₂ and CeO₂ impurity is inevitable in Ce-doped Li₄Ti₅O₁₂ materials. As we designed, Li₄Ti₅Ce_0.1O₁₂ with Ce interstitial doping has the bigger lattice volume than Li₄Ti_4.9Ce_0.1O₁₂ with Ce substitution doping and pristine Li₄Ti₅O₁₂. As for the electrochemical performance, Li₄Ti₅Ce_0.1O₁₂ delivers the highest capacity at 0.2 C (over 170 mAh g⁻¹) and best rate performance among the pristine and Ce-doped Li₄Ti₅O₁₂ materials. Ac impedance results show that the …