A novel network composite cathode was prepared by mixing LiFePO 4 particles with multi-walled carbon nanotubes (MWCNTs). LiFePO 4 particles were connected by MWCNTs and a polymer binder, polypyrrole–polyethylene glycol (PPy–PEG), to form a three-dimensional network. The surface morphology and thermal stability of the LiFePO 4 –MWCNT/PPy–PEG composite cathode were investigated by scanning electron microscopy, thermogravimetric analysis and pyrolysis capillary gas chromatography. It was found by scanning electron microscopy that the particle size of LiFePO 4 in the LiFePO 4 –MWCNT sample was smaller than that of the pure LiFePO 4 and the structure in the LiFePO 4 –MWCNT/PPy–PEG sample was more homogeneous than in the LiFePO 4 –MWCNT/PPy sample. Thermogravimetric analysis indicated that PPy-PEG blend polymer in combination with MWCNTs considerably improves the thermal stability of the final cathode material. Pyrolysis capillary gas chromatography measurements at 500°C showed a decreased thermal stability of organic species contained in the composite cathode material. The addition of MWCNTs was an effective way to increase homogeneity and thermal stability of the LiFePO4–MWCNT/PPy–PEG cathode material.[New Carbon Materials 2013, 28(1): 1–7]