The interaction of TbCl3 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 Tb3+ in ethanolic solution of TbCl3 significantly increased owing to the excitation energy transfer from PVP to Tb3+ ions, which was more efficient as compared to a direct excitation of the Tb3+ 4f75d1 levels. In contrast, emission of NEt4Tb(hfa)4 and NEt4Eu(hfa)4 complexes was almost completely quenched in solution containing PVP. The PVP bound both Ln3+ ions and hfa ligands which caused decomposition of Ln-hfa complexes and switched off the excitation energy transfer from the ligand to the emitting Ln3+ ion. The important role of hydrogen bonds in stabilization of interaction of hfa ligands with PVP was indicated. The interaction of TbCl3 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 Tb3 + in ethanolic solution of TbCl3 significantly increased due to excitation energy transfer from PVP to Tb3 + ions, which was more efficient as compared to a direct excitation of the Tb3 + 4f75d1 levels. In contrast, emission of NEt4Tb (hfa) 4 and NEt4Eu (hfa) 4 complexes was almost completely quenched in solution containing PVP. The PVP bound both Ln3 + ions and hfa ligands which caused decomposition of Ln-hfa complexes and switched off the excitation energy transfer from the ligand to the emitting Ln3 + ion. The important role of hydrogen bonds in stabilization of interaction of hfa ligands with PVP was indicated .