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An easy solid-state method is used to prepare Li2ZnTi3O8 (LZTO) doped by the Nb element (LZTN1O). Nb-doping not only improves the specific surface area, total pore volume, and ionic conductivity but also reduces the particle size and transfer resistance of LZTN1O. In addition, the structure has been stabilized, and good electrical contact has been obtained for the LZTN1O electrode via Nb-doping. Compared with LZTO, the electrochemical performance of LZTN1O at 0–55 °C is greatly improved. After 600 cycles, 99.1% of the capacity for the second cycle is obtained at 25 °C at 1 A g–1. For the current densities up to 2–4 A g–1, no capacity loss based on the specific capacity of the second cycle occurs at the 200th cycle at 25 °C. At 3 A g–1, 180.8 mA h g–1 is delivered at the 120th cycle. At 1 A g–1 for 55 °C, no capacity is lost (corresponding to the second cycle) after 100 cycles. At 0.8 A g–1 for 0 °C, 178.8 mA h g–1 can be obtained for the 60th cycle, and even no capacity is lost (corresponding to the second cycle) for the 500th cycle at 0.5 A g–1. Moreover, when LZTN1O was applied in the LiMn2O4/LZTN1O full cell, the initial discharge specific capacity based on the mass of LiMn2O4 is 90.2 mA h g–1 at 0.5 C in 2.1–3.8 V.