In this paper, we constructed an ordered self-organized film possessing a well-defined layered structure by using a polymerizable surfactant-encapsulated polyoxometalloeuropate, (DMDA)(9)EuW10O36 (DMDA: dodecyl(11-methacryloyloxyundecyl)dimetliylammonium bromide). The in situ polymerization of the film through UV irradiation was investigated by using H-1 NMR and FTIR spectra, and X-ray diffraction. The results show that 68% of the monomers that connect to the complex in the film have been polymerized at the utmost. In contrast to the virgin layered structure of the casting film which possesses a layer spacing of 2.7 nm, the layer thickness increases to about 3.3 nm after the in situ polymerization. The lifetime and the quantum yield of the polyoxometalate in the casting film were found to increase due to the change of the layered structure after in situ polymerization. Thus, the present results provide an effective way to tune the photophysical Properties of the film through alteration of the layered structure. In the meantime, the stability of the casting film in the alkaline solution was improved after in situ. polymerization. (C) 2008 Elsevier Inc. All rights reserved.