3-(N-Carbazolyl)-l-propyne polymerized with MoCl5- and WCl6-based catalysts to produce a polymer in high yields. The MoCl5 and MoCl5-n-Bu4Sn catalysts were the most effective (the systems solidified immediately after initiation of polymerization with these catalysts). The product polymer was a yellow solid insoluble in any solvent. Copolymerization of the present monomer with tert-butylacetylene by MoCl5-n-Bu4Sn produced a copolymer; it had a high molecular weight (M(w) 350,000), completely dissolved in toluene, CHCl3 etc, and formed a free-standing film by solution casting. omega-N-Carbazolyl-l-hexyne and -l-octyne produced toluene-insoluble polymers with WCl6-Ph4Sn.