LiFePO4/C composite materials were synthesized by a solid-state method. The carbon source was selected from glucose, cauric acid, cinnamic acid and PVA and the influence of different carbon sources on the performances of LiFePO4/C was investigated. The crystal structure, morphology and electrochemica1 properties of LiFePO4/C were analyzed by XRD, SEM and galvano static charge-discharge method. The results show that the materials have olivine structure and that the LiFePO4 material coated with carbon gives enhanced performance in terms of practical capacity and cycleability of the cell with lithium metal piece as an anode. The specimen used PVA as the carbon source has a fine and uniform particle size and shows excellent electrochemical performances. The first discharge capacity is up to 147.5 mAh•g-1 at 0.1C rate, and after 20 times of cycling the discharge capacity is still 144.7 mAh•g-1.