A new methodology is proposed by which the number of coordinated water molecules, n, can be estimated in Eu3+ complexes. It is based on a comparison between the theoretical and experimental Stark levels, the former being calculated by assuming that n varies from 0 to 4 and predicting the so-called ligand field parameters, B-q(k). The methodology, initially developed in the study of the Eu(pya)(3)center dot nH(2)O complex, has been applied successfully to beta-diketonate complexes of Eu3+, for which crystallographic and luminescence data are available.