Abstract: The polyaniline/tungsten carbide(PANI/WC) composite is synthesized by in situ polymerization using aniline and ammonium persulfate as starting materials. The conductivity on the tungsten carbide content is studied in detail, and the proper polymerization condition is obtained. The structure and stability of the composites are characterized by FT-IR spectra，XRD，XPS and DSC-TGA analysis. The results show that the electrical conductivity is enhanced obviously due to the introduction of WC to PANI. PANI in the composites is amorphous and the crystal structure of WC is unchanged compared with the initial WC. The thermal stability and protonation degree of composites are excellent.