A simple organic solvent based sol-gel method for synthesis of carbon-coated LiFePO4 is developed. Phase pure LiFePO4 with uniform size of 200–300 nm and no agglomeration is obtained, with 1.8 wt % surface carbon formed in-situ. Such a material gives specific discharge capacities of 150 mAh/g and 145 mAh/g at C/5 and 2C at room temperature, respectively, with desirable cycling stability. The dependence of particle size and morphology on precursor concentrations is opposite to conventional solution based methods. Other LiMPO4 (M = Mn, Co, Ni, etc) with favorable physical characteristics can be synthesized the same way.