Three new layered metal-organic frameworks (MOFs) based on 2-phenylsuccinic acid (H 2 psa) and lanthanide ions, with formula [Ln 2 (C 10 H 8 O 4 ) 3 (H 2 O)] (Ln= Eu, Sm and EuGd) have been synthesized under solvothermal conditions and fully characterized by singlecrystal X-ray diffraction, thermal and vibrational analysis. The compounds are isostructural featuring 2D frameworks that consist of infinite zig-zag chains composed by [LnO 8 ] and [LnO 8 (H 2 O)] edge-sharing polyhedra linked by psa ligands leading to layers further connected by weak π-π interactions in an edge orientation. Moreover, a topological study was carried out to obtain the simplified net for better comparison with structurally related compounds. The Eupsa crystals were exfoliated into nanolayers after miniaturization by addition of sodium acetate as capping agent in the reaction medium. Scanning electron microscopy was applied to characterize the miniaturized samples whereas the exfoliated hybrid nanosheets were studied by atomic force microscopy. The photoluminesce (PL) properties of the bulk compounds as well as the miniaturized and exfoliated materials were investigated and compared with other related ones. An exhaustive study of the Eu(III)-based MOFs was performed on the basis of the obtained PL parameters (excitation and emission spectra, k r , k nr , intrinsic quantum yields and lifetimes) to explore the underlying structure-property relationships.