The thermal behavior and thermodynamic properties of europium tris(hexafluoroacetylacetonate) Eu(hfa)3 and the mixed-ligand 4-cyanopyridine-N-oxide complex [Eu(hfa)3(cpo)] were investigated by thermal analysis and Knudsen effusion mass spectrometry. The compounds sublime congruently. The composition of the gas phase over the compounds and the partial pressures of the components were determined. The enthalpies of sublimation, polymerization, and dissociation of these compounds were derived from experimental data.