Fluorine is the most electronegative element and can be used as an excellent hydrogen-bond acceptor. Fluorous coordination compounds exhibit several advantageous properties, such as enhanced high thermal and oxidative stability, low polarity, weak intermolecular interactions and a small surface tension compared to hydrocarbons. C-H...F-C interactions, although weak, play a significant role in regulating the arrangement of the organic molecules in the crystalline state and stabilizing the secondary structure. Two cadmium(II) fluorous coordination compounds formed from 2,2'-bipyridine, 4,4'-bipyridine and pentafluorobenzoate ligands, namely catena-poly[[aqua(2,2'-bipyridine-κN,N')(2,3,4,5,6-pentafluorobenzoato-κO)cadmium(II)]-μ-2,3,4,5,6-pentafluorobenzoato-κO:O'], [Cd(CFO)(CHN)(HO)], (1), and catena-poly[[diaquabis(2,3,4,5,6-pentafluorobenzoato-κO)cadmium(II)]-μ-4,4'-bipyridine-κN:N'], [Cd(CFO)(CHN)(HO)], (2), have been synthesized solvothermally and structurally characterized. Compound (1) shows a one-dimensional chain structure composed of Cd-O coordination bonds and is stabilized by π-π stacking and O-H...O hydrogen-bond interactions. Compound (2) displays a one-dimensional linear chain structure formed by Cd-N coordination interactions involving the 4,4'-bipyridine ligand. Adjacent one-dimensional chains are extended into two-dimensional sheets by O-H...O hydrogen bonds between the coordinated water molecules and adjacent carboxylate groups. Moreover, the chains are further linked by C-H...F-C interactions to afford a three-dimensional network. In both structures, hydrogen bonding involving the coordinated water molecules is a primary driving force in the formation of the supramolecular structures.