For the first time, we observed photoluminescence in Eu(III) dithiocarbamate complexes at room temperature-more specifically in [Eu(Et2NCS2)(3)phen], [Eu(Et2NCS2)(3)bpy] and the novel [Eu(Ph2NCS2)(3)phen], where phen stands for 1,10-phenanthroline and bpy for 2,2'-bipyridine. Correlations between the electronic structure of the dithiocarbamate ligands on one hand, and covalency, intensity, and ligand field spectroscopic parameters on the other, could be established. Moreover, the relative values of the emission quantum efficiencies obtained for these complexes, as well as their dependence with temperature, could be satisfactorily described by a theoretical methodology recently developed.