The LiMnPO4/C composite material was synthesized via a sol-gel method based on the citric acid. The X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance tests were adopted to characterize the properties of LiMnPO4/C. The XRD studies show that the pure olivine phase LiMnPO4 can be obtained at a low temperature of 500 °C. The SEM analyses illustrate that the citric acid used as the chelating reagent and carbon source can restrain the particle size of LiMnPO4/C well. The LiMnPO4/C sample synthesized at 500 °C for 10 h performs the highest initial discharge capacity of 122.6 mA-h/g, retaining 112.4 mA-h/g over 30 cycles at 0.05C rate. The citric acid based sol-gel method is favor to obtain the high electrochemical performance of LiMnPO4/C.