Charge transfer multiplayer films have been prepared by layer-by-layer self-assembly technique. The films incorporate the rare-earth-containing polyoxometalate K-11[Eu{PW11O39}(2)](.)nH(2)O and the rich electron polyelectrolyte poly(3-viny-1-methyl-pyridine) quaternary ammonium and display a linear increase in the absorption and film thickness with the number of deposition cycles. Ultraviolet and visible absorption spectra, atomic force micrographs, small-angle X-ray reflectivity measurements, and photoluminescence spectra were used to determine the structure of films. Linear and regular multilayer growth was observed. We can observe the formation of charge transfer complex compound in multiplayer by layer-by-layer assembly method. Most importantly, the luminescence spectra show the charge transfer band in assembly films, which suggest that energy could be effectively transferred to rare earth ions in assembly multiplayer films. (c) 2004 Elsevier B.V. All rights reserved.