Carboxylic-acid derivatives of butadiyne and octatetrayne including ester and amide were prepared and solid-state polymerizability was investigated. Though octatetrayne derivatives and most of carboxylic acid and amide derivatives of butadiyne can be polymerized, no esters of butadiyne show polymerizability irrespective of success in crystal growth up to centimeter order. X-ray crystallographic analysis of three esters pointed out weak intermolecular interaction in these derivatives resulting in molecular packing which is based on space filling only.