Three novel Cd(II)/Zn(II) compounds, [Cd 2 (poda) 2 (phen) 3 (H 2 O)] n ·nEtOH·3nH 2 O(1), [Zn(poda) 2 (bpy)(H 2 O)] n (2) and [Zn(Hpoda) 2 (bpy)](3) (H 2 poda=1,2-phenylenediacetic acid, phen=1,10-phenanthroline, bpy=2,2′-bipyridyl), have been synthesized and characterized by IR, TG, fluorescent spectrum and single-crystal X-ray diffraction techniques. In 1, poda 2− anions link the adjacent Cd(II) centers to generate a 1D zigzag chain. Furthermore, an unprecedented four-footed “8-shaped” mixed water–ethanol (H 2 O) 6 (C 2 H 5 OH) 2 cluster connects four double chains based on 1D zigzag chain into 3D supramolecular architecture. By bis(chelate–monodentate) fashion of poda 2− ligand, compound 2 exhibits 1D zigzag chains, which forming a dense zipper-like 2D structure via strong π–π stacking interactions. Differed from 1 and 2, compound 3 has a mononuclear motif, and displays a 3D 6-connected α-Po net hydrogen-bonded topology. The structure-related solid-state fluorescence spectra of compounds 1 and 2 have been determined.