The solvothermal reactions of terphenyl-2,5,2′,5′-tetracarboxylic acid (H₄tptc) and transition metal cations (Ni^II, Mn^II) afford five novel coordination polymers (CPs) in the presence of four bis(imidazole) bridging ligands (1,3-bimb = 1,3-bis(imidazol-1-ylmethyl)benzene, 1,4-bmib = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, 4,4′-bibp = 4,4′-bis(imidazol-1-yl)biphenyl, 4,4′-bimbp = 4,4′-bis(imidazol-1-ylmethyl)biphenyl), namely, [M(tptc)_0.5(1,3-bimb)(H₂O)]_n (M = Ni for 1, Mn for 2), {[Ni(tptc)_0.5(1,4-bmib)]·0.25H₂O}_n (3), {[Ni(tptc)_0.5(4,4′-bibp)₂(H₂O)]·2H₂O}_n (4) and {[Ni(tptc)_0.5(4,4′-bimbp)_1.5(H₂O)]·H₂O}_n (5). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes 1 and 2 are isomorphous and exhibit a 3D (3,4)-connected tfi framework with the point Schläfli symbol of (4·6²)(4·6⁶·8³). Complex 3 shows an unprecedented 3D (4,4)-connected framework with the point Schläfli symbol of (4·6⁴·8²)₂(4²·8⁴). Complex 4 displays a novel 2D self-catenating 5-connected network with the Schläfli symbol of (4⁶·6⁴) based on three interpenetrating 4⁴-sql subnets. Complex 5 features a 2D 3-connected 6³-hcb network built from interesting chains with loops. To the best of our knowledge, the 3D (4,4)-connected (4·6⁴·8²)₂(4²·8⁴) host-framework of 3 and 2D self-catenating 5-connected (4⁶·6⁴) network of 4 have never been documented to date. Moreover, the UV-Visible absorption spectra of complexes 1–5 have been investigated.