Pure olivine LiFePO 4 /C composite compounds are synthesized by carbothermal reduction (CTR) method using trigonal anhydrous FePO 4 raw material. The physical and electrochemical properties of the prepared samples are investigated in comparison with those of a sample obtained from incompletely crystallized hydrous FePO 4 ·2H 2 O. The olivine LiFePO 4 /C prepared with trigonal anhydrous FePO 4 has a high discharge capacity of 142mAhg −1 at 0.1C. The composite also displays a better rate capability, a higher discharge capacity and a more stable cycle-life than that synthesized with incompletely crystallized hydrous FePO 4 ·2H 2 O. The improved electrochemical performance of trigonal anhydrous FePO 4 synthesis samples originates mainly from the single-phase structure and small particle size.