The first example of 3D heterometallic 4d–4f 2,7-naphthanlenedisulfonate compounds [LnAg2(2,7-NDS)(IN)3] (Ln=Sm (1), Eu (2), Gd (3), Tb (4), Dy(5); 2,7-NDS=2,7-naphthanlenedisulfonate; IN=isonicotinic acid) has been synthesized via hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analyses, FT-IR spectroscopy, powder X-ray diffraction(PXRD) and thermogravimetric analyses (TGA). X-Ray structural analysis reveals that compounds 1–5 exhibit same well-organized 3D coordination frameworks that are built up by 2D elliptical cylinder shaped [LnAg2(2,7-NDS)(IN)3] layers which are constructed by 1D anionic chains [Ln(2,7-NDS)(IN)3]2− linking the adjacent Ag(I) ions, and [LnAg(μ2-O)2] units, possessing a 7-connected topology with the Schläfli symbol of {33;411;56;6}. Furthermore, the luminescence properties of compounds 2 and 4 and the magnetic properties of compounds 3 and 5 were investigated.