Olivine structure of lithium iron phosphate (LiFePO4) has been recognized to be the most promising cathode material for electric vehicle due to its high theoretical capacity, outstanding thermal stability, and excellent cycling stability. Nano/micro porous structure LiFePO4/C composites were synthesized by wet milling-spray drying-carbothermal reduction method. X-ray diffraction (XRD), scanning electron microscopy (SEM), were used to determination the morphological structure of materials, constant current charge-discharge test is used to determination the effects of calcination conditions on the electrochemical performances of LiFePO4/C. The results show that: sintered at 650 ℃ for 8.5 h, the sample delivered a discharge capability of 123 mAh?g-1 with no capacity loss after 100 cycles at 10 C under room temperature, showing better discharge capability and cycle performance, these advantages were useful for the application of power batteries.