Lithium iron phosphate-carbon (LiFePO4/multiwalled carbon nanotubes (MWCNTs)) composite cathode materials were prepared by a hydrothermal method. In this study, we used MWCNTs as conductive additive. Poly (vinylidene fluoride-co-hexafluoropropylene)-based solid polymer electrolyte (SPE) was applied. The structural and morphological performance of LiFePO4/MWCNTs cathode materials was investigated by X-ray diffraction and scanning electron microscopy/mapping. The electrochemical properties of Li/SPE/LiFePO4-MWCNTs coin-type polymer batteries were analyzed by cyclic voltammetry, ac impedance and galvanostatic charge/discharge tests. Li/SPE/LiFePO4-MWCNTs polymer battery with 5 wt % MWCNTs demonstrates the highest discharge capacity and stable cyclability at room temperature. It is indicated that LiFePO4-MWCNTs can be used as the cathode materials for lithium polymer batteries. Copyright © 2011 John Wiley & Sons, Ltd.