A facile and practical route was introduced to prepare LiFePO4/C cathode material with nano-sized primary particles and excellent electrochemical performance. LiH2PO4 was synthesized by using H3PO4 and LiOH as raw materials. Then, as-prepared LiH2PO4, reduced iron powder and alpha-D-glucose were ball-milled, dried and sintered to prepare LiFePO4/C. X-ray diffractometry was used to characterize LiH2PO4, ball-milled product and LiFePO4/C. Differential scanning calorimeter-thermo gravimetric analysis was applied to investigate possible reactions in sintering and find suitable temperature for LiFePO4 formation. Scanning electron microscopy was employed for the morphology of LiFePO4/C. As-prepared LiH2PO4 is characterized to be in P21cn(33) space group, which reacts with reduced iron powder to form Li3PO4, Fe-3(PO4)(2) and H-2 in ball-milling and sintering. The appropriate temperature for LiFePO4/C synthesis is 541.3-976.7 degrees C. LiFePO4/C prepared at 700 degrees C presents nano-sized primary particles forming aggregates. Charge-discharge examination indicates that as-prepared LiFePO4/C displays appreciable discharge capacities of 145 and 131 mA . h . g(-1) at 0.1 and 1 C respectively and excellent discharge capacity retention.