AbstractA series of new tris(pyrazolyl)borate (Tp−) and tris(2‐pyridylpyrazolyl)borate (TpPy−) Eu3+, Gd3+, Tb3+ and Dy3+ complexes with the dianionic ligand 4,4′‐bis(2‐sulfonatostyryl)biphenyl (Ssp2−, a widely used fluorescent whitener) were synthesized and their luminescence properties were studied. The Gd3+, Tb3+ and Dy3+ compounds possess only ligand‐centered emission, arising from the Ssp2− ligand, with quantum yields of up to 60 %. While the emission centers in these complexes are similar, the positions of the luminescence maxima, the emission quantum yields, and the lifetimes change in the order [(Tp2Ln)2Ssp]<[(TpPyLnSsp)2]<[Ln2Ssp3]n. Among the complexes studied, Eu3+‐centered emission was observed for only [(Tp2Eu)2Ssp]. In this compound, Tp− plays the role of an antenna ligand for Eu3+‐radiation, though the quantum yield is only 5 %.