Six new metal−organic frameworks (MOFs) with structures ranging from a one-dimensional (1D) chain, two-dimensional (2D) layer, even 2D double layer to three-dimensional (3D) network based on 2,2′bipyridine-3,3′-dicarboxylate-1,1′-dioxide (H 2 bpdado) and N-donor ligands (1,2-bis(4-pyridyl)ethane (bpa) or 1,2-trans-bis(4-pyridyl)ethene (bpe)), namely, [Cd(bpdado 6), were synthesized by hydro(solvo)thermal and/or diffusion methods. In these complexes, the bpdado ligand shows four types of coordination modes, three of which appeared for the first time. Polymers 1−6 present diverse motifs with different metal ions and different conformations and/or coordination modes of bpdado, which may show a natural synergy in structural diversity of the resultant MOFs. Under the similar synthetic conditions just with different metals (Cd(II) and Pb(II)), 6 exhibits a 2D covalent grid layer, whereas complex 1 displays a 1D chain. Meanwhile, Cd(II) atom in 1 shows an unprecedented triangular prism coordination geometry. Although bpe/bpa ligands act as pillars between 2D [M(bpdado)] n layer subunits in complexes 2−5, the Cd(II)-based complexes 2 and 3 are extended into a 3D layered-pillared network, while the Pd(II)-based complexes 4 and 5 just exhibit the 2D double layers. Moreover, the 2D [Cd(bpdado)] n layer subunits of 2 and 3 can be derived from replacing hydrogen bonds in 1D 1 with coordination bonds dependent on different coordination modes of bpdado. In addition, the solid-state luminescence (for 1−6) and gas adsorption properties (for 2 and 3) have been studied and discussed in detail.