[M(XeF2)(5)](PF6)(2) (M = Ca, Cd) complexes were prepared by the reaction of MF2 and XeF2 under pressure of gaseous PF5 in anhydrous HF as solvent. The coordination sphere of the Ca atom consists of nine fluorine atoms: three from two PF6- units (one bidentate and one monodentate) and one from each of six XeF2 molecules. The coordination sphere of the Cd atom consists of eight fluorine atoms: one from each of two PF6- units and one from each of six XeF2 molecules. Two of the XeF2 ligands about M in each compound are bridging ligands and are each linked to two M, generating infinite (-M-F-Xe-F-M-F-Xe-F-) chains along the b-axis in the Ca salt and along the c-axis in the Cd compound. The Cd2+ cation is smaller and more electronegative than the Ca2+ cation. These differences account for the higher F ligand coordination in the Ca2+ salt and for other structural features that distinguish them. The different stoichiometry of the PF6- salts when compared with their AsF6- analogues, which have the composition [M(XeF2)(4)](AsF6)(2) (M = Ca, Cd), is in accord with the lower F ligand charge in the AsF6- when compared with that in the PF6- compound. Indeed, the AsF6- ligand charges appear to be similar to those in the XeF2-bridged species.