A new compound with the formula [Eu-4(ETA)(9)(OH)(3)(H2O)(3))], where ETA is ethyl 4,4,4-trifluoroacetoacetate, has been synthesized and investigated by photoluminescence spectroscopy. The compound was characterized by means of chemical analysis, vibrational (IR), UV-vis absorption, and luminescence spectroscopies, and X-ray crystallography. The crystal structure of the [Eu-4(ETA)(9)(OH)(3)(H2O)(3))] complex in the solid state, determined by X-ray diffraction analysis, revealed that it crystallizes in the triclinic crystal system, space group P (1) over bar, with four crystallographically independent europium centers. From these structural data, the ground-state geometry of the tetramer has been calculated by using the Sparkle/AM1 model. The emission spectrum shows the characteristic transitions of the Eu3+ ion. The features displayed by the(5)D(0) -> F-7(0) transition in the emission spectrum are consistent with the Eu3+ ion occupying four different sites in chemical environments of low symmetries, in agreement with the X-ray data and the optimized geometry obtained from the Sparkle/AM1 model. These structural results have allowed the theoretical calculation of 4f-4f intensity parameters, including the forced electric dipole and dynamic coupling mechanisms as well as ligand singlet and triplet states, in good agreement with experiment.