A cationic spiropyran iodide derivative (SPI) was synthesized as a photoresponsive compound, and SPI/montmorillonite clay hybrid films were prepared using ion- and guest-exchange intercalation methods. When the ion-exchange method was applied to clay with a low cation-exchange capacity (CEC) intercalation, of SPI into clay interlayers did not occur. Using the clay with a high CEC SPI was intercalated into clay interlayer and the interlayer distances were elongated. Upon UV and visible light irradiation, SPI in hybrid film photoisomerized reversibly and the interlayer distance also changed reversibly. On the other hand, intercalation by the guest-exchange method using cethyltrimethylammoniumbromide (CTAB) as a preexchanging reagent was independent on the CEC. After the addition of SPI, the CTAB in the clay interlayers was exchanged for SPI, but a partial CTAB remained in the interlayer. SPI in the hybrid films prepared by the guest-exchange method photoisomerized reversibly without any change in interplanar distance due to the coexisted CTAB. (C) 2009 Elsevier B.V. All rights reserved.