Novel acetylene monomers containing carbazolymethyl groups, 3,5-bis[(3,6-di-t-butyl)carbazolylmethyl]-1-ethynylbenzene (1), 3-(3,6-di-t-butyl)carbazolylmethyl-1-ethynylbenzene (2), and 4-(3,6-di-t-butyl)carbazolylmethyl-1-ethynylbenzene (3) were synthesized, and polymerized with [(nbd)RhCl] 2 –Et 3 N, Rh + (nbd)[η 6 -C 6 H 5 B − (C 6 H 5 ) 3 ], and WCl 6 -n-Bu 4 Sn catalysts. The corresponding polyacetylenes with number-average molecular weights ranging from 1600 to 115,000 were obtained in 18%-quantitative yields. The UV–vis absorption band edge wavelengths of the polymers obtained with W catalyst were longer than those of the Rh-based polymers. The photoluminescence quantum yields of the W-based polymers were 1.1–3.1%, while those of the Rh-based ones were 0.18–4.1%.