Pure olivine LiFePO4 can be successfully prepared with co-precipitation from aqueous solution containing trivalent iron ion. The introduction of hydrolyzed sugar before heating give the best result, because the poor conductivity of the powders can be improved by synthesizing small and homogeneous powders with coatings of electronically conductive materials. The resultant LiFePO4/C composite with carbon scaffold and LiFePO4 embedded can achieve high specific capacity (143mAhg−1) after the 100th cycle with 1C charge/discharge rate at 50°C. The excellent cycle life and stability as well as cheap precursor solution make the process feasible commercially. Moreover, since the only auxiliary product of thermal treatment in this process is water vapor, the process is more environmental friendly than other synthesized methods.