Novel carbazole-containing acetylene monomer, 1-(3-ethynyl-9-carbazoyl)-4-(9-carbazoyl)benzene 1 was synthesized, polymerized, and copolymerized with phenylacetylene (PA) using [(nbd)RhCl](2)-Et3N, Rh+(nbd)[(6)-C6H5B-(C6H5)(3)], and WCl6-Ph4Sn as catalysts. Polymers with number-average molecular weights ranging from 7800 to 33,200 were obtained in 60%-quantitative yields. The absorption band edge of poly(1-co-PA) (1:PA=8:2) was positioned at a wavelength longer than those of 1 and polyvinylcarbazole. Poly(1-co-PA) (1:PA=8:2) emitted fluorescence with 60% quantum yield. Poly(1-co-PA) (1:PA=8:2) worked as a hole transport material of an OLED with tris(8-hydroxyquinoline)aluminum (Alq3) as an emission material. (c) 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015, 53, 1245-1251