Four new coordination polymers, namely [Co(H₂O₂abtc)(bibp)]_n (1), {[Mn_1.5(Oabtc)(H₂O)₂]·(H₂bmib)_0.5·H₂O}_n (2), {[Cd_1.5(O₂abtc)]·(H₂bmib)_0.5·2H₂O}_n (3), and {[Cd(nip)(bibp)]·0.5H₂O}_n (4),were constructed under solvothermal conditions in the presence of two bis(imidazole) bridging linkers (bimb = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, bibp = 4,4′-bis(imidazol-1-yl)biphenyl). The unstable azo ligand of 3,3′,5,5′-azobenzenetetracarboxylic acid (H₄abtc) could be oxidized and resulted in three oxidized derivatives of H₄Oabtc (one N atom was oxidized), H₄O₂abtc (two N atoms were oxidized), and H₂nip (one H₄abtc was oxidized to two 5-nitroisophthalic acids). Their structures were determined by single-crystal X-ray diffraction and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complex 1 exhibited an interestingly 2D + 2D → 3D parallel entangled network based on 4-connected (4⁴·6²)-sql sheets. Complex 2 was found to be a {Mn₃(COO)₆} trinuclear SBU based 2D (3,6)-connected (4³)₂(4⁶·6⁶·8³)-kgd sheet. While complex 3 displays a {Cd₃(COO)₈} trinuclear SBUs based 3D (4,8)-connected (4⁶)₂(4¹²·6¹²·8⁴)-flu network. Complex 4 can be regard as a {Cd₂(COO)₂} binuclear SBUs based 6-connected (4⁴·6¹¹)-6T8 framework. In addition, the magnetic property of complexes 1, 2 and the luminescence properties of complexes 3, 4 were investigated.