Solvothermal reactions of flexible 1,2-phenylenedioxydiacetic acid (H 2 PDA) or hydroquinone-O,O′-diacetic acid (H 2 QDA) with zinc nitrate or cadmium nitrate in the presence of auxiliary 1,1′-(1,4-butanediyl)bis(imidazole) (BBI) ligand gave rise to four coordination polymers, namely, {[Zn(PDA)(BBI)]·3H 2 O} n (1), {[Zn(PDA)(BBI)]·DMF} n (2), {[Cd 2 (QDA)(BBI)]·4H 2 O} n (3), [Cd(QDA)(BBI)] n (4). All the compounds were characterized by elemental analysis, IR and single-crystal X-ray diffraction methods. Compound 1 exhibits a puckered (2D) (4, 4) grid net with a Schlafli symbol of 4 4 6 2 . Compound 2 has the dinuclear Zn 2 (PDA) 2 “loops” which are further connected by BBI ligands into 2D sheet along (01−1) plane with a Schlafli symbol of 2.6 5 . Interestingly, the Zn 2 (PDA) 2 “loops” are penetrated by BBI ligands of the other equivalent net. Thus an unusual 2D polyrotaxane-like structure is formed containing rotaxane-like motifs. Compound 3 possesses a three-dimensional (3D) diamond-type network with a Schlafli symbol of 6 6 . Compound 4 has the dinuclear cadmium core as the node and shows a 3D threefold interpenetrating 8-connected uninodal network with a Schlafli symbol of 3 6 4 18 5 3 6. The structural differences of these complexes give some insights into the effect of solvent on the construction of coordination polymers with the same components under solvothermal conditions. In addition, the fluorescent properties of 1–4 were also investigated.