A series of polypyrrole-LiFePO4 (PPy-LiFePO4) composites were synthesised by polymerising pyrrole monomers on the surface of LiFePO4 particles. AC impedance measurements show that the coating of polypyrrole significantly decreases the charge-transfer resistance of LiFePO4 electrodes. The electrochemical reactivity of polypyrrole and PPy-LiFePO4 composites for lithium insertion and extraction was examined by charge/discharge testing. The PPy-LiFePO4 composite electrodes demonstrated an increased reversible capacity and better cyclability, compared to the bare LiFePO4 electrode.