LiMn2O4 submicro-rods are synthesized via solid-state reaction by using γ-MnOOH submicro-rods as self-template, which is prepared via a solvothermal process in the presence of ethanol/water solvent by using KMnO4 and MnCl2 as raw materials. It is found that the ethanol content in a certain ethanol/water volume ratio range has no obvious influence on the crystal phase and morphology of γ-MnOOH submicro-rods derived from the solvothermal process, and a proper solid-state reaction temperature range for the preparation of spinel LiMn2O4 submicro-rods by using γ-MnOOH submicro-rods as self-template is 500∼700°C. Moreover, the effects of reaction temperature on structure, crystal phase and electrochemical performance of the obtained LiMn2O4 submicro-rods as cathode material of Li-ion battery are studied in detail, and the LiMn2O4 submicro-rods obtained at 600°C exhibit the best electrochemical performance with an initial capacity of 125.6 mAh g−1 and 95.6% capacity retention after 100 cycles at 3C. Importantly, the rod-like nanostructure and crystal phase can be well preserved after prolonged the charge/discharge cycling time at a relatively high current rate, indicating its good structural stability as cathode material. Further development of this γ-MnOOH submicro-rod self-templating method may be interesting for the commercial production of LiMn2O4 for Li-ion batteries with superior high-rate capability and good cycling stability.