Six novel coordination polymers (CPs) based on a rigid tridentate ligand, 4′-(4-(imidazol-1-yl)phenyl)-4,2′:6′,4′'-terpyridine (imphtpy), namely {[Zn2(imphtpy)2(p-bdc)2]·(H2O)}n (1), [Zn(imphtpy)(m-bdc)]n (2), {[Zn(imphtpy)(qda)1.5]·(H2O)}n (3), [Cd2(imphtpy)2(m-bdc)2]n (4), [Cd(imphtpy)(abtc)0.5]n (5) and [Cd(imphtpy)(qda)]n (6), (p-H2bdc = 1,4-benzenedicarboxylic acid, m-H2bdc = 1,3-benzenedicarboxylic acid, H2qda = hydroquinone-o,o'-diacetic acid and H4abtc = 3,3′,5,5′-azobenzenetetracarboxylic acid), have been solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis and single-crystal X-ray diffraction. Complex 1 displays a pseudo four-fold interpenetration of dia network in a [2 + 2] mode. Complex 2 exhibits a 2D → 2D polycatenane of two-fold interpenetrated network with the sql topology. Complex 3 shows a interdigitated 2D layer with the sql topology, which is further extended into a 3D supramolecular framework through π-π interactions and hydrogen bonds. Complex 4 features a two-fold interpenetrated (4,4)-connected 3D + 3D → 3D framework with the bbf topology. Complex 5 reveals a 2D network constructed by binuclear Cd2(CO2)4 secondary building unit (SBU) with the sql topology which is further packed into a 3D supramolecular framework through π-π interactions. Complex 6 is a 3D network constructed by binuclear Cd2(CO2)2O2 SBU with the uninodal 6-c pcu topology. These results indicate that the versatile coordination networks of imphtpy and various polycarboxylate ligands play crucial roles in modulating the structural topologies of coordination networks. In addtion, photoluminescence properties have been explored for complexes 1–6 in the solid state at room temperature, which are derived from metal perturbed intraligand charge transfer (ICT) or ligand-to-ligand charge transfer.