Polyacetylene is the most hopeful electrical conductive polymer, which is being exploited to fabricate plastic battery, solar energy cell etc. The catalysts used for the synthesis of high cis-polyacetylene films are mainly Ti(OC_4H_9)_4-AlEt_8 and rare-earth coordination catalysts as well as Co(NO_3)_2-NaBH_4. This paper reports features of acetylene polymerization by novel catalysts composed of transition metal 2-ethyl hexyl phosphonates of the fourth periodic transitional series-Ti, V, Cr, Mn, Fe, Co, Ni and aluminium trialkyls. Except Ni catalyst system, all catalytic systems can promote polymerization of acetylene at room temperature to form a silvery-grey polyacetylene film with rich cis-content and high crystallinity. Under the experimental conditions tested, the catalytic activity of various systems shows the following sequence: Fe>Ti～V>Cr>Mn>Co>Ni The polyacetylene films obtained were characterized. Polyacetylene is the most hopeful electrical conductive polymer, which is being exploited to fabricate plastic battery, solar energy cell etc. The catalysts used for the synthesis of high cis-polyacetylene films are mainly Ti (OC_4H_9) _4-AlEt_8 and rare earth accelerators This paper reports features of acetylene polymerization by novel catalysts composed of transition metal 2-ethyl hexyl phosphonates of the fourth periodic transitional series-Ti, V, Cr, Mn, Fe, Co, Ni and aluminum trialkyls. All catalytic systems can promote polymerization of acetylene at room temperature to form a silvery-gray polyacetylene film with rich cis-content and high crystallinity. Under the experimental conditions tested, the catalytic activity of various systems shows the following sequence: Fe> Ti-V> Cr> Mn> Co> Ni The polyacetylene films obtained were characterized.