Rod-like orthorhombic LiMnO2 nanocrystals were successfully synthesized using temperature-controlled microwave hydrothermal route (TCMH) in a short time (30min) at a temperature as low as 160°C. o-LiMnO2 obtained by two different methods was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemistry test. SEM revealed that the product obtained in case of TCMH was rod-like with a diameter of 40nm, while the nanoparticles with 200nm diameter were obtained by traditional hydrothermal route (TH). The dramatic formation of o-LiMnO2 in the microwave hydrothermal field influenced the morphology and crystal structure of the final products. The formation and preferred growth orientation mechanism of o-LiMnO2 in the microwave irradiation process was discussed. Electrochemistry performance exhibited that the as-synthesized o-LiMnO2 nanorods reached the maximum discharge capacity of 194.2mAhg−1 at 0.1C rate after several cycles between 2.2 and 4.4V vs. Li+/Li at room temperature, which was higher than the electrochemical performance of o-LiMnO2 obtained by TH. The experimental results showed that the TCMH method provided an effective way for preparing o-LiMnO2 cathode material in lithium-ion batteries.