A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl24H2O as the Fe2+ source. SEM and TEM show that the LFP micro hollow spheres have a quite uniform size of 1 m consisting of aggregated nanoparticles. The influences of solvent and Fe2+ source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe2+ ions was firstly proposed based on the XRD transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coated a uniform carbon layer 3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101 and even 72 mAh g-1 at 0.1C, 1C, 5C, 20C and 50C, respectively. It could also maintain 80 % the initial discharge capacity after cycling for 2000 times at 20 C.