Abstract Five transition metal compounds containing arenesulfonates and 4,4′-bipy ligands, namely [Zn2(N,N′-4,4′-bipy)(N-4,4′-bipy)2(H2O)8](bpds)2 · 5H2O (1), [Ag2(N,N′-4,4′-bipy)2(bpds)] (2), [Cd(N,N′-4,4′-bipy)(H2O)4]2(4-abs)4 · 5H2O (3), [Cu(N,N′-4,4′-bipy) (O-bs)2(H2O)2] · 4H2O (4), and [Zn(N,N′-4,4′-bipy)2(H2O)2](4,4′-bipy)(bs)2 · 4H2O (5) (4,4′-bipy = 4,4′-bipyridine, bpds = 4,4′-biphenyldisulfonate, 4-abs = 4-aminobenzenesulfonate, bs = benzenesulfonate), have been synthesized and characterized by X-ray single crystal diffraction, elemental analyses and TG analyses, in order to investigate the coordination chemistry of arenesulfonates and 4,4-bipy, as well as to construct novel coordination frameworks via mixed-ligand strategy. Compounds 2, 4 and 5 could be obtained via hydrothermal or aqueous reactions. Compound 1 forms a binuclear octahedral metal complex. Compounds 2–4 form polymeric chains. Compound 5 consists of 2D square grids with one intercalated 4,4′-bipy molecule. Weak Ag–Ag interactions are observed in compound 2. These complexes show great structural varieties and there are three different coordination modes observed for both the 4,4′-bipy and the sulfonate ligands.