Cu 2 (dpds) 2 (C 5 O 5 ) 2 (H 2 O) 4 ]•3H 2 O (1), [Cu(dpds)(C 5 O 5 )]•3H 2 O (2), and [Cu 2 (dpds) 2 (C 5 O 5 ) 2 ]•9H 2 O•C 2 H 5 OH (3) (dpds = 4,4′-dipyridyldisulfide and C 5 O 5 2− (croconate) = dianion of 4,5-dihydroxycyclopent-4ene-1,2,3-trione), have been synthesized and structurally characterized. Compound 1 contains two crystallographically independent Cu(II) ions, which are both distorted octahedral geometry with elongation along the croconate-and H 2 O-bound axial positions and bonded with two N atoms of two dpds, two O atoms of one C 5 O 5 2−, and two H 2 O molecules. Two crystallographically independent dpds ligands, both adopting the bismonodentate bridging mode, connect two Cu(II) ions to form a onedimensional zigzag chain-like coordination polymer. In 2 and 3, there are two and three crystallographically independent Cu(II) ions, respectively, which are all distorted octahedral geometries with elongation along the croconate-bound axial positions six-coordinated and bonded with two N atoms of two dpds ligands in cis-or/and trans-forms and four O atoms of two C 5 O 5 2− ligands. The dpds ligands in 2 and 3 all adopt the bis-monodentate bridging mode, and the C 5 O 5 2− ligands act as bridging ligands with bridging bis-bidentate through three C 5 O 5 2− oxygen atoms in 2 and bridging bis-bidentate through four adjacent C 5 O 5 2− oxygen atoms in 3, respectively, linking the Cu(II) ions to generate a two-dimensional layered and a three-dimensional metal−organic framework, respectively. The structural diversity and dimensionality observed in 1−3 may be attributed to the cis-or/and trans-coordination sphere of Cu(II) centers with two dpds ligands and the coordination modes of croconate ligands. Thermal stability and in situ temperature-dependent structural variations of 1−3 have been verified by thermogravimetric analysis and powder X-ray diffraction measurements. Compounds 1 and 3 both exhibit water vapor capture behaviors with hysteresis isotherms.