Six new Co(ii)-based mixed-ligand coordination polymers, namely, [Co2(H3bppc)2(2,2'-bpy)4]·H2O (), [Co2(Hbppc)(2,2'-bpy)2(H2O)]·H2O (), [Co(H2bppc)(H-bpp)]·2H2O (), [Co3(μ3-OH)(bppc)(dps)(CH3CH2OH)]·4H2O (), [Co2(bppc)(bib)(H2O)4]·(H2-bib)0.5·(H2O)3 (), and [Co2(Hbppc)(bix)2]·2H2O (), (H5bppc = biphenyl-2,4,6,3',5'-pentacarboxylic acid, 2,2'-bpy = 2,2'-bipyridine, bpp = 1,3-bis(4-pyridyl)propane, dps = 4,4'-sulfanediyldipyridine, bib = 1,4-bis(imidazol-1-yl)benzene, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), have been obtained under solvothermal conditions. exhibits a 3D supramolecular framework based on a [Co2(H3bppc)2(2,2'-bpy)4] unit. has a (3,4)-connected dmc net with a (4·8(2))(4·8(5)) topology containing alternate binuclear metal clusters and single metal centres. shows a 3D supramolecular architecture constructed from ladder-like arrays decorated with H-bpp. exhibits a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)](5+) units with an unusual (3·4(6)·5(2)·6)(3(2)·4(6)·5(7)·6(5)·7) topology. features a (4,6)-connected 3D fsc open framework with binuclear [Co2(H2O)(COO)](3+) units as nodes, and H2-bib and water molecules located in the voids of its framework by hydrogen bonds. possesses a 3D net containing unusual 2D polyrotaxane sheets. Topological analysis reveals that has a (3,4,4)-connected 3D network with a (4·6·7(4))(4·6·7)(6·7(2)·10(2)·11) topology. The structural difference of and is due to the different pH values of the reaction system. Though complexes were synthesised under similar reaction conditions, the carboxylic groups of H5bppc were partially deprotonated in , and and fully deprotonated in and . Complexes display diverse structures depending on different N-donor ligands and the coordination modes of the multicarboxylate ligand. Variable-temperature magnetic susceptibility measurements reveal that complexes show antiferromagnetic interactions.