Luminescence, excitation of luminescence, IR and Raman spectra of europium acetates with 1,10-phenanthroline derivatives (Ph), Eu(CH 3 COO) 3 .Ph, were studied. Crystal field parameters for model complexes were calculated. Some conclusions about details of the structure of the compounds were obtained. It was shown that both steric hindrances due to ligand–ligand crowding and donor–acceptor properties of the ligands are significant in creation of the structure. Maximum inequivalence of Eu–O bonds in compound containing 5-nitro-phenanthroline with electrophilic NO 2 -group was noted as well as in compounds with 3,4,7,8-tetramethyl- and 5-phenyl-phenanthroline having bulky substituents. There is the strongest polarisation of the carboxyl groups in these compounds. Nearly equalised Eu–O bonds were found in compound with 4,7-diphenyl-phenanthroline. Here a steric factor was minimised due to rotation of phenyl radicals in relation to the phenanthroline nucleus.