Ultrathin multilayer films of a polyoxotungstoeuropate cluster K-15[Eu(BW11O39)(2)](Eu(BW11)(2)) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The Eu(BW11)(2)/PAH multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each Eu(BW11)(2) adsorption. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(0) --> F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent multilayers with polyoxometalates (POMs). (C) 2002 Elsevier Science B.V. All rights reserved.