The solvothermal reactions of 1,1'-oxybis[3,5-di-4-pyridine]-benzene (L) and transition metal cations (Co and Ni) afford five novel coordination polymers in the presence of flexible bridging ligands (4,4'-H2nba = 4,4'-dicarboxydiphenylamine, H2cam = d-camphoric acid, 4,4'-H2sdb = 4,4'-sulfonyldibenzoic acid, H2chdc = 1,4-trans-cyclohexanedicarboxylic acid), namely {[Co2L2(OH)2(nba)]·2DMF}n (), {[CoL(cam)(H2O)]}n (), {[Co3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), {[Ni3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), and {[Ni2L2(chdc)2(H2O)2]·(H2O)3}n () (DMF = N,N-dimethylformamide). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and powder X-ray diffraction. Complex reveals a 2-fold interpenetrating three-dimensional (3D) framework with the Schläfli symbol {4·8·10(4)}{4·8·10} topology. Compound crystallizes in the achiral space group with the d-camphorate ligand racemized. Compounds and reveal similar structure with the {3·4(4)·6}{3(2)·4(8)·5(9)·6(9)} topology based on a linear trinuclear building block M3(OOCR)6 (M = Co(ii) or Ni(ii)). Compound is a wavy sheet, where both carboxylate and L ligands act as bidentate ligands. Moreover, UV-Visible absorption spectra of complexes , and the magnetic properties of have been investigated.