In this study, the PCDA derivative (HEEPCDA) with hydroxyl group was synthesized and used to form the cast film with PVA. This film was fabricated by drying the HEEPCDA vesicle in PVA solution. After polymerization of HEEPCDA, the multilayered cast films were formed with polymerized HEEPCDA layer and PVA layer alternately. The XRD results revealed the formation of regular layered structure with thickness of 52.6–59.8 Å. It is proposed that the PVA layers between HEEPCDA layers hold the HEEPCDA layers strongly due to presence of hydrogen bonding. We tried to change the fabricating method for the cast film to get the fine regular structure in this study. Among the formed cast films, only one cast film which got the fine regular repeating structure demonstrated very fast reversible chromatic response to the thermal cycle. We proved that the fabricating method for cast film is important to get the fast color transition character in this study