N-Substituted carbamic acid esters of 8-pyridyl-5,7-octadiyn-1-ol were synthesized and all the monomers showed solid-state polymerizabilities by UV irradiation to give polydiacetylenes with pyridyl groups directly bound to the pi-conjugated backbone. Hydrogen-bond complexes of these monomers with dodecanoic acid (DA) or perfluorododecanoic acid (PFDA), in which the pyridyl nitrogen atom formed a hydrogen bond with the hydrogen atom of the carboxyl group, were also prepared. Although complex formability of DA with the monomers in this study was not so high, many PFDA complexes were obtained because of the higher acidity. All complexes could be polymerized in the solid state and the conversion increased by complexation compared with the original monomers. More favorable monomer stacking for solid-state polymerization could be achieved by combination of intermolecular hydrogen bonds between urethane groups and alkyl (or perfluoroalkyl) chain packing.