Abstract: The high cis-polyacetylene filmis with metallic appearance were synthesized by new coordination catalysts composed of Fe(naph), or Fe(P204)₃ or Fe(P507)₃ and aluminum trialkyl at room temperature.The resultant polyacetylene was charac-terized by IR, ESR, X-ray diffraction, SEM, TEM, electrical resistivity measurement and elemental analysis. The higher activity of polymerization and direct forming films of polyacetylene having rich cis-content were obtained with these catalysts.The single crystal and spot diagram from electron diffraction of polyaCetyl-ene prepared with the Fe(P507)₃ system were found. Electrochemistry and batteryof polyacetylene were studied too.