A group of new carbazole-containing polyacetylenes, poly[n-(9-carbazolyl)-1-alkynes] [m = n - 2; m = 3 (P2a), 9 (P2b)], poly[5-(3,6-dibromo-9-carbazolyl)-1-pentyne] (P3a), and poly[n-(9-carbazolyl)-1-chloro-1-alkynes] [m = n - 2: m = 3 (P4a), m = 9 (P4b)], have been synthesized using WCl6-Ph4Sn and MoCl5-Ph4Sn as catalysts. High molecular weight (up to 500 000) polymers have been obtained in high yields (up to 80%). The molecular structures of the polymers are characterized by spectroscopic methods. All the monomers except (P2a) are highly luminescent. The polymer with a long spacer length (P2b) emits intense deep-blue light when excited at 295 nm.