Tungsten trioxide micropheres were prepared by spray pyrolysis, and tungsten carbide microspheres were produced by spray pyrolysis-low temperature reduction and carbonization technology. Multi-walled carbon nanotube-tungsten carbide composites were prepared by the continuous reduction and carbonization process using multi-walled carbon nanotubes (MWCNTs) and WO3 precursor by molecular level mixing and calcination. The morphology and structure of the samples were characterized by scanning electron microscope and transmission electron microscope. Furthermore, the crystal phase was identified by X-ray diffraction. The electrocatalytic activity of the sample was analyzed by means of methanol oxidation. Tungsten carbide microspheres were catalytic active for methanol oxidation reaction. Nevertheless tungsten trioxide microspheres and multi-walled carbon nanotube-tungsten carbide composites were not catalytic active for methanol oxidation reaction. These results indicate that tungsten carbide micropheres are promising catalyst for methanol oxidation. Tungsten trioxide micropheres were prepared by spray pyrolysis, and tungsten carbide microspheres were produced by spray pyrolysis-low temperature reduction and carbonization technology. Multi-walled carbon nanotube-tungsten carbide composites were prepared by the continuous reduction and carbonization process using multi-walled carbon nanotubes (MWCNTs) and WO3 precursor by molecular level mixing and calcination. The morphology and structure of the samples were characterized by scanning electron microscope and transmission electron microscope. Furthermore, the crystal phase was identified by X-ray diffraction. The electrocatalytic activity of the sample Tungsten carbide microspheres were catalytic active for methanol oxidation reaction. Tungsten carbide oligomers were catalytic active for methanol oxidation reaction. e micropheres are promising catalyst for methanol oxidation.