Well-prepared pristine Li2ZnTi3O8 has a great potential to be employed as anode material, which possesses a lager lithium intercalation capacity and excellent rate performance for Li-ion batteries because of its higher electronic conductivity. To obtain an optimal preparation condition, the Li2ZnTi3O8 anode materials were prepared and annealed in air and nitrogen atmospheres for comparison. To our surprise, Li2ZnTi3O8 materials annealed in nitrogen atmosphere exhibits excellent stable cycling life and rate performance indicated by a higher reversible capacity of 181.9 mAh g−1 over 100 cycles at 2000 mA g−1 because it can introduce the oxygen defect and improve the intrinsic electronic conductivity. These superior electrochemical performances are primarily attributed to the ameliorated electronic conductivity, which derives from the change of Ti valence from +4 to +3. Besides, a novel LiNi0.5Mn1.5O4/Li2ZnTi3O8 full cell is configured and it exhibits good rate capacity under 2.0–4.6 V at different charge rates and discharged at 2.0 A g−1. This full cell system exhibits excellent capacity at the high charge and discharge rates and it could be suitable candidate for application in the large capacity storage devices. Moreover, it can also be widely used in the field of the fast charge and discharge electronic products.