Since solid-state polymerization reaction of symmetrically-substituted octatetrayne derivatives can start from both 1,4- and 5,8-positions in the same column of the monomers in crystals, deterioration of crystallinity seemed to occur to some extent in the course of polymerization. Thus, an asymmetrically-substituted octatetrayne, i.e. 13-(4-butyl-2,3,5,6-tetrafluorophenyl)-6,8,10,12-tridecatetraynyl N-(butoxycarbonylmethyl)-carbamate (5BCMU-4A-BTFP), was synthesized and its polymerization site was examined using high resolution solid-state (13)CNMR spectroscopy. And it was shown that asymmetrical substitution of octatetrayne is effective for site-selective 1,4-addition polymerization. Absorption spectrum and third-order nonlinear optical properties of the 5BCMU-4A-BTFP polymer were also investigated.