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Li₄Ti₅O₁₂ (LTO), a “zero-strain” anode material for lithium-ion batteries, exhibits excellent cycling performance. However, its poor conductivity highly limits its applications. Here, the structural stability and conductivity of LTO were studied using in situ high-pressure measurements and first-principles calculations. LTO underwent a pressure-induced amorphization (PIA) at 26.9 GPa. The impedance spectroscopy revealed that the conductivity of LTO improved significantly after amorphization compared with its starting phase. Furthermore, our calculations demonstrated that the different compressibility of the LiO₆ and TiO₆ octahedra in the structure was crucial for the pressure-induced amorphization. The amorphous phase promotes Li⁺ diffusion and enhances its ionic conductivity by providing defects for ion migration. Our results not only provide an insight into the pressure depended structural properties of a spinel-like material but also facilitate exploration of the interplay between pressure-induced amorphization and conductivity.