A new type of octacoordinated ternary β-diketonates complexes of terbium and europium has been prepared using the anionic tetradentate terpyridine-carboxylate ligand (L) as a sensitizer of lanthanide luminescence in combination with two β-diketonates ligands 2-thenoyltrifluoroacetyl- acetonate (tta-) for Eu3+ and trifluoroacetylacetonate (tfac-) for Tb3+. The solid state structures of the two complexes [Tb(L)(tfac)2] (1) and [Eu(L)(tta)2] (2) have been determined by X-ray crystallography. Photophysical and 1H NMR indicate a high stability of these complexes with respect to ligand dissociation in solution. The use of the anionic tetradentate ligand in combination with two β-diketonates ligands leads to the extension of the absorption window toward the visible region (390 nm) and to high luminescence quantum yield for the europium complex in the solid state (Φ = 66(6)%). Furthermore, these complexes have been incorporated in polymer matrixes leading to highly luminescent flexible layers. © 2013 American Chemical Society.