Diacetylene derivative, 1,6-bis(3-nonyl-9-carbazolyl)-2,4-hexadiyne was designed and synthesized. Compared with nonsubstituted 1,6-di(N-carbazolyl)-2,4-hexadiyne, the solubility was drastically unproved, which allowed us the fabrication of a smooth crystalline thin film via a simple spin-coating process. The resulting film was easily polymerized by photoirradiation after thermal annealing. UV-vis absorption and Raman scattering spectra suggested topochemical polymerization. Out-of-plane XRD measurement of spin-coated film showed a strong diffraction. It suggests the interdigitation structure of alkyl chain. In-plane XRD measurements of spin-coated polymerized films showed two small peaks which were not identical to the result of out-of-plane XRD. These results indicated edge-on orientation. AFM image suggests that the film is composed of an aggregation consisting of needle-like nanostructures of polymer crystals.