Two new hybrid compounds with cadmium cations/coordination complexes as linkers, (C 6 H 5 NO 2 ) 4 -[(H 2 O) 14 Cd 3 (CrMo 6 H 6 O 24 ) 2 ] 1 (C 6 H 5 NO 2 = pyridine-4-carboxylic acid) and H[(H 2 O) 2 (C 6 H 5 NO 2 )(C 6 H 4- NO 2 )Cd] 2 [CrMo 6 H 6 O 24 ]ร9H 2 O 2 (C 6 H 5 NO 2 , C 6 H 4 NO 2 = pyridine-3-carboxylic acid), have been synthesized and characterized by elemental analyses, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the polar space group Pc and is made up of [CrMo 6 H 6 O 24 ] 3ร polyoxoanions covalently linked by cadmium cations to yield an unprecedented one-dimensional chain, which represents the first example of one-dimensional assemblies based on Anderson-type POMs and cadmium cations. Adjacent inorganic chains are further in close contact by pyridine-4-carboxylic acid glues to form three-dimensional supramolecular polar networks via strong hydrogen-bonding interactions. Compound 2 exhibits a three-dimensional supramolecular channel framework constructed from cationic cadmium-pyridine-3carboxylic acid coordination polymer sheets pillared by Anderson-type polyoxoanions, with dissociated water molecules situated in the channels. Furthermore, both of the compounds exhibit photoluminescent properties at ambient temperature.