The synthesis, luminescence properties, experimental determination and theoretical calculation of the emission quantum yield of Eu(NTA)3.2L complexes, where NTA is naphtoiltri-fluroacetone and L denotes H2O or DMSO (dimethyl sulphoxide), were reported. The compounds were characterized by elemental analysis (carbon, hydrogen and europium), thermal analysis, UV-visible absorption and photoluminescence spectroscopies. The experimental quantum yields were determined based on a method previously proposed by Bril and collaborators. The Eu(NTA)3.2DMSO compound shows a high value for the Ω2 intensity parameter (35.8 × 10−20 cm2), reflecting the hypersensitive nature of the 5D0 → 7F2 transition and indicating that the lanthanide ion is in a highly polarizable chemical environment. The experimental quantum yield measured for that compound, 0.75, is one of the highest so far reported for solid-state europium complexes. The theoretical calculations of the quantum yield were carried out by solving an appropriate set o...