A series of metal–organic complexes based on d10 metals and the ligand H4bbh (H4bbh = benzene-1, 2, 4, 5-biformhydrazide), formed through hydrothermal in situ acylate reaction of H4bta (H4bta = benzene-1, 2, 4, 5-tetracarboxylic acid) with hydrazine hydrate (N2H4·H2O), have been prepared and structurally characterized by single-crystal X-ray diffraction. Compounds [Zn(μ2-H2bbh)(phen)(H2O)]2 (1) (phen = 1, 10-phenanthroline) and [Zn(μ2-H2bbh)(2, 2′-bpy)]2 (2) (2, 2′-bpy = 2, 2′-bipyridine) are both dinuclear complexes in which bridging ligands H2bbh2− display different μ2- coordination modes. [Zn(μ2-H2bbh)1/2(μ2-H2bbh)1/2(H2O)]n (3) exhibits a two-dimensional (2-D) layer structure containing simultaneously two kinds of different coordination modes of H2bbh2−: μ2-bidentate and μ4-tetradentate. [Cd(μ3-H2bbh)(phen)]n (4) consists of one-dimensional (1-D) double-metal chains. The crystal structures of these compounds are stabilized by hydrogen bonds and π⋯π interactions, forming three-dimensional supramolecular networks. All of the compounds were characterized by IR, UV-vis spectra and elemental analysis and they show good fluorescence properties in the solid state at room temperature. In order to understand the emission mechanism, we carried out TDDFT calculations on the excited electronic states of compound 2.