Li2ZnTi3O8 (LZTO) was synthesized by solid-state reaction using TiO2-anatase, Li2CO3, Zn(CH3COO)2·2H2O as raw materials. Three well-designed modified samples including LZTO-K (keqin black), LZTO-M (carbon microspheres) and LZTO-S (super-P) were prepared by extra adding carbon materials as loose and porous agent in the synthesis process without any crystal structure change. Among the all samples, LZTO-M exhibits excellent electrochemical performances in terms of high capacities (209.6, 187.2, 178.0, 161.8, 154.4 mAh g−1 at current densities of 0.1, 0.5, 1.0, 2.0, 3.0 A g−1, respectively) after 100 circulations and shows remarkable stable cycling performance, retaining capacity of 133.6 mAh g−1 compared with that (82.6 mAh g−1) of LZTO over 500 cycles at 3.0 A g−1. The utilization of carbon microspheres not only reduces particle size of LZTO-M and makes particles well-distributed, but also promotes loose structure with uniform porous and increases the surface area.