The single crystalline LiMn2O4 rods are synthesized by solid state reaction at varying temperatures (450 °C and 550 °C) using γ-MnOOH rods as self-templates, which are obtained by a typical hydrothermal process. X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electrochemical tests are thoroughly conducted/performed to investigate its structure and properties. XRD, SEM and TEM observations show that LiMn2O4 spinel-type powders have good crystallinity and similar rods morphology with the width of 300–400 nm and the length of 500 nm–5 μm. As the cathode material for lithium batteries, LiMn2O4 synthesized at 450 °C delivers higher initial discharge capacity of 123.2 mA h g−1 at 0.1C and retains 84.0 mA h g−1 after 500 cycles at 10C rate. Even at a high current density of 40C, the material still presents an excellent discharge capability of 95.2 mA h g−1. The probable effect of structure and prepared-temperature is analyzed in detail.