Three mixed-ligand coordination polymers, [Cu(oda)(2,2'-bipy)](2) (1), Ni(2)(oda)(2)(4,4'-bipy)·DMF (2), and [{Ni(oda)(H(2)O)(2)}(2)(μ-4,4'-bipy)]·2H(2)O (3) were synthesized and characterized. Complex 1 features a 1D chain via intermolecular π-π interactions. Complex 2 is a novel 3D microporous coordination polymer with 1D polarized channels. Complex 3 forms a 3D network via extensive hydrogen bonding interactions. Thermogravimetric analyses have been studied. The chemical sensing properties have been investigated in situ by quartz crystal microbalance (QCM). Complex 1 has a good sensitivity to toluene, complexes 2 and 3 have exceptionally high selectivity and sensitivity to water over organic solvents.