The layer-by-layer (LbL) self-assembly technique was successfully applied to the fabrication of dye-polyoxometalate. multilayer composite films consisting of two dye molecules Rhodamine B (RB) and Rhodamine 6G (R6G) and a Keggin-type polyoxometalate [alpha-SiW12O40](4-) (alpha-SiW12). The composite films were characterized by UV-vis spectroscopy, scanning electron microscopy (SEM), and fluorescence spectroscopy. UV-vis spectra show that the characteristic absorbance values of the multilayer films increase almost linearly with the number of dye/alpha-SiW12 bilayers, suggesting that the deposition process is regular and highly. reproducible fro. in layer to layer. SEM micrographs indicate that the film surface is a little rough with some individual granular domains. In addition, the fluorescent properties of these composite films were also investigated by fluorescence spectroscopy. (c) 2004 Published by Elsevier B.V.