The X‐ray crystal structures of the polyfluorinated complexes [5,5′‐bis(HCF2CF2CF2CF2CH2OCH2)‐2,2′‐bpy]MI2 (55‐8F‐PtI2 and 55‐8F‐PdI2 where M = Pt and Pd, respectively) were obtained. These two structures are found to show not only two different types of intramolecular, six‐membered cyclic C–H···F–C interactions (F2C–H···F–C and HC–H···F–C) as important structural features but also alternating fluorinated and non‐fluorinated layers. The F2C–H···F–C interactions, which are close to the metal core, are much better structurally characterized in this type of complexes with fluorous ponytails at the 5,5′ positions than those previously reported at the 4,4′ positions. The molecular planes of (bpy)MI2 are extended by self‐matching, using two C–H···I hydrogen bonds and one C–H···F–C blue‐shifting hydrogen bond. The F2C–H···F–C hydrogen bonds interact at the supramolecular level such that one polyfluorinated ponytail of the title compounds is transoid without an intramolecular C–H···F–C interaction, while the other polyfluorinated ponytail is cisoid with an intramolecular C–H···F–C interaction. Why one ponytail is cisoidal while the other is transoidal will be explained. Furthermore, the second type of C–H···F–C interactions involving the methylene H atom has been identified for the first time. In addition, these two metal structures are studied by density functional theory (DFT).
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