A simple chemical oxidative polymerization of pyrrole (Py) directly onto the surface of LiFePO4 particles was applied to the synthesis of polypyrrole-LiFePO4 (PPy-LiFePO4) powder. The LiFePO4 sample without carbon coating was synthesized by a solvothermal method. The polyethylene glycol (PEG) was used as additive during Py polymerization for increasing the PPy-LiFePO4 conductivity. Properties of resulting LiFePO4, PPy-LiFePO4 and PPy/PEG-LiFePO4 samples were characterized by XRD, SEM , TGA and galvanostatic charge-discharge measurements. These methods confirmed the presence of polypyrrole on LiFePO4 particles and its homogeneous distribution in the resulting powder material. The PPy/PEG-LiFePO4 composites show higher discharge capacity than pure LiFePO4, as PPy/PEG network improves the electron conductivity. It presents specific discharge capacity of 153 mAh/g at C/5 rate. (C) 2009 Elsevier Ltd. All rights reserved.