Aniline was polymerized on the surface of LiFePO4 particles by in-situ polymerization technique, forming LiFePO4/polyaniline composites. The composites were characterized by Thermo gravimetric analysis, specific surface area tests, high resolution transmission electron microscopy observation. The specific capacity, rate capability and cycling stability of composites were studied by charge-discharge tests. The experimental results show that the LiFePO4/polyaniline composite containing 6.75% polyaniline possesses the best electrochemical properties. Its initial capacity reaches 151.97 mAh.g-1 at C/10 rate, its cycling stability is excellent, its specific capacity is 124.89 mAh.g-1 at 1 C rate, its capacity loss is only 17.82% when rate increased from C/10 to 1 C.