The interaction of TbCl 3 and lanthanide(III) β-diketonate complexes with poly(N-vinylpyrrolidone) (PVP) polymer was studied using fluorescence spectroscopy. In the presence of PVP the emission of Tb 3+ in ethanolic solution of TbCl 3 significantly increased owing to the excitation energy transfer from PVP to Tb 3+ ions, which was more efficient as compared to a direct excitation of the Tb 3+ 4f 7 5d 1 levels. In contrast, emission of NEt 4 Tb(hfa) 4 and NEt 4 Eu(hfa) 4 complexes was almost completely quenched in solution containing PVP. The PVP bound both Ln 3+ ions and hfa ligands which caused decomposition of Ln-hfa complexes and switched off the excitation energy transfer from the ligand to the emitting Ln 3+ ion. The important role of hydrogen bonds in stabilization of interaction of hfa ligands with PVP was indicated.