Ten coordination compounds, namely {[Cd(L)(die)]·2/3H2O}n (1), [Cd(L)(dib)]n (2), [Cd(L)(bmimb)]n (3), {[Cd(L)(bimb)]·1/2EtOH}n (4), [Zn(L)(bimb)]n (5), [Co(L)(bimb)]n (6), {[Cd(L)(phen)]·EtOH}n (7), [Cu(L)(phen)]n (8), [Zn(L)(mtpy)]n (9) and [Ni(L)(mtpy)]·1/2H2O (10) (H2L=4′-((2-carboxyphenoxy)methyl)biphenyl-2-carboxylic acid, die=1,2-di(1H-imidazol-1-yl)ethane, dib=1,4-di(1H-imidazol-1-yl)butane, bmimb=1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, bimb=1,4-bis((1H-imidazol-1-yl)methyl)benzene, phen=1,10-phenanthroline and mtpy=4′-(4-methylphenyl)-2,2′:6′,2″-terpyridine), have been solvothermally synthesized. These compounds were characterized by X-ray crystallography, elemental analysis, infrared spectra (IR) and powder X-ray diffraction (PXRD). In compounds 1–3, similar dimeric [Cd2(L)2] units are connected by different N-donor ligands to form diverse architectures. Strikingly, compound 3 displays a 2D→3D interdigitated framework. Compounds 4–6 are essentially isostructural and reveal 2D sheet structures. Compound 7 shows a 2D 44-sql network stabilized by π–π interactions between the pyridine rings of the phen ligands. Compound 8 exhibits a 3D supramolecular architecture constructed from a 1D chain via π–π interactions. Compound 9 possesses a 1D chain structure, which is further extended into a 2D supramolecular layer through hydrogen-bonding interactions. Compound 10 displays a [Cd2(L)2(mtpy)2] dimeric structure. Adjacent dimers further interact through hydrogen-bonding interactions to afford a 1D supramolecular chain. Moreover, the luminescent properties of 1–5, 7 and 9 have also been investigated in this work.