Four coordination polymers, namely {[Zn(L) 2 ](ClO 4 ) 2 } n (1), [Zn(L)(ipa)] n (2), [Cd(L)(chdc)⋅2H 2 O] n (3) and [Cd(L) 0.5 (pydc)⋅0.5H 2 O] n (4) (H 2 ipa=isophthalic acid, H 2 chdc=cyclohexane-1,4-dicarboxylic acid, H 2 pydc=pyridine-2,6-dicarboxylic acid), have been synthesized based on a flexible ligand 1,2-bis(pyridin-3-yloxy)ethane (L) under hydrothermal conditions. Their structures are determined by X-ray single-crystal analyses, IR spectra and X-ray powder diffractions (XRPD). In 1, the infinite 2D square sheets arrange regularly to form 1D channels containing ClO4- anions. 2 exhibits wave-like network, which is further extended into a 3D framework via interlayer C−H⋯X (X=π, O) interactions. With different co-ligands, 3 shows a 2D structure, while 4 exhibits a intriguing 3D supramolecular framework. In 1–4, L adopts different conformations in the solid state. The various conformations of L, with the different co-ligands, play an important role in structural diversity. The thermogravimetric analyses and photoluminescent properties of them were also investigated.