A photochromic diarylethene, 1,2-bis(2-methyl-5-p-methoxyphenyl-3-thienyl)perfluorocyclopentene (1a), forms four kinds of polymorphic crystals by recrystallization from the hexane solution. X-ray crystallographic analysis of the needle crystals among four polymorphic forms indicated that the diarylethene is orientated into herringbone nanolayered structures. The crystal exhibited photochromism upon photoirradiation. Alternate nanolayered structures composed of open- and closed-ring isomers were formed by irradiation with polarized visible light after irradiation with ultraviolet light.