Two kinds of europium-beta-diketone chelates, binary Eu(DBM)(3) and temary Eu(DBM)(3)phen were doped in poly(methyl methacrylate) (PMMA). These chelates show very different photoluminescent (PL) behaviors: the hypersensitive D-5(0) --> F-7(2) emission bands of Eu(DBM)(3)phen change slightly with the molar ratios, while those of Eu(DBM)(3) change obviously and regularly with the molar ratios. The results of the luminescent lifetimes of D-5(0) levels show that the binary chelate exists as two kinds of species in the doped systems, and the lifetimes and contents of each species change with the molar ratios, while the ternary chelate exists as one kind of species in the doped systems. X-ray diffraction (XRD) patterns of the binary chelate doped systems give some diffraction peaks that are different from those of pure chelate and change with the molar ratios, indicating new kinds of crystal structures formed, and consequently, the first coordination sphere of Eu3+ ion changes; while those of the ternary chelate doped systems just show amorphous diffraction halos of the host, indicating that the ternary chelate exist in an amorphous state and disperse well in the host. The FTIR spectra of PMMA also change gradually with increasing the molar ratios of the doped two kinds of chelates, and the XRD patterns show that the amorphous halos of PMMA in the doped systems are different from those of pure PMMA and change with the molar ratios, too, suggesting the interaction between the guest and the host. (C) 2003 Elsevier B.V. All rights reserved.