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lithium titanium-based oxides have been demonstrated as good anode materials for lithium-ion batteries. These materials perform at safe operating potential of the electrolyte, but suffer from low energy density. Here, we reported a new type titanium-based anode material, Li₂TiGeO₅, for lithium-ion batteries, which delivers a reversible specific capacity of 691 mA h g⁻¹ and 68% initial coulombic efficiency under a current density of 0.02 A g⁻¹, with operational potential of 0.5 V vs. Li/Li⁺. The experiments, including in-situ X-ray diffraction, in-situ Raman spectra, synchrotron-based X-ray absorption spectroscopy, coupled with first-principles calculations, demonstrated multi-electron reaction during discharge/charge process. The lithiation products including electronic conducting TiO and Li–Ge alloy simultaneously with Li-ion conducting Li₂O provide good electrochemical performances of Li₂TiGeO₅ anode in …