A series of structurally related rigid imidazole ligands, 1,4-bis(imidazol-1-yl)benzene (L1), 1,4-bis(benzoimidazol-1-yl)benzene (L2), and 4,4′-bis(benzoimidazol-1-yl)biphenyl (L3), have been utilized to construct coordination polymers. The reactions of CdX2 (X = BF4− or ClO4−) with these ligands afford three new three-dimensional networks, {[Cd(L1)3](BF4)2(CHCl3)2}∞ (1), {[Cd(L2)3](ClO4)2(CHCl3)4(CH3OH)2}∞ (2), and {[Cd(L3)3](ClO4)2}∞ (3). Compounds 1−3 are all α-Po metal−organic frameworks (MOFs) based on six-connected CdII nodes which are octahedrally coordinated by six nitrogen atoms of ligand molecules. Complex 2 represents a distorted α-Po framework with noninterpenetration, whereas 1 and 3 both exhibit a double interpenetrating α-Po network. These results suggest that the degree of interpenetration is tunable by ligand modifications, that is, varying the ligand spacer or terminal group. The three complexes exhibit a different void volume in their network. Gas adsorption measurements indicate that 3 possesses moderate gas-adsorption ability for CO2, and the progress of adsorption and desorption is reversible.