Two lead(II) compounds [Pb3(idiac)3(phen)2(H2O)]·2(H2O) (1) and [Pb(ndc)]n (2), where H2idiac=iminodiacetic acid, phen=1,10-phenanthroline and H2ndc=naphthalene-2,6-dicarboxylic acid, have been synthesized and structurally characterized. Single crystal X-ray diffraction analysis showed that compound 1 is a discrete trinuclear complex (of two-fold symmetry) which evolves to a supramolecular 3D network via π–π interactions, while in compound 2 the naphthalene dicarboxylate anion act as a linker to form a three dimensional architecture, where the anion adopts a bis-(bidentate bridging) coordination mode connecting four Pb(II) centers. The photoluminescence property of the two complexes has been studied.