A new series of lanthanide metal–organic frameworks, namely, [Ln (L) (bpdc) 0.5 (phen)] ∞ (Ln=Eu (1), Gd (2), Tb (3), Dy (4); L=4,4′-bis(2-sulfonatostyryl)biphenyl; bpdc=4,4′-biphenyldicarboxylate; phen=1,10-phenanthroline), has been synthesized hydrothermally from the self-assembly of the lanthanide ions (Ln 3+ ) with the fluorescent whitener disodium 4,4′-bis(2-sulfonatostyryl)biphenyl (Na 2 L), the 4,4′-biphenyldicarboxylic acid (H 2 bpdc) and 1,10-phenanthroline. All of them were characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis and single-crystal X-ray diffraction. To the best of our knowledge, this is the first time to use the Na 2 L to synthesize LMOFs in coordination bonds binding fashion. Structural analyses reveal that all four complexes have isostructural three-dimensional (3D) net-structures. Complexes 1–4 display intriguing fluorescent properties and the photoluminescent properties of 1 were discussed in detail.