A series of ruthenium and osmium complexes containing highly fluorous diphosphine ligands FPPF = (F13C6C6H4-p)2P(CH2)2P(p-C6H4C6F13)2 (dfppe) and (F13C6C6H4-p)2P(CH2)3P(p-C6H4C6F13)2 (dfppp) has been prepared. The fluorous diphosphine ligands incorporate four C6F13 “fluoro-ponytails”, and these have been effective in solubilizing the complexes in supercritical carbon dioxide (scCO2). Precise solubility measurements in scCO2 were performed for some of the complexes. The new complexes [MX2(FPPF)2] and [MX(FPPF)(η-C5H5)], M = Ru, Os, X = Cl, Br, have been characterized by a number of spectroscopic techniques and their electrochemical properties measured, three of the ruthenium complexes also being characterized by single-crystal X-ray studies. The noncovalent interactions observed in the X-ray structures have been analyzed by the Hirshfeld surface approach, putting them on a more solid footing. The fluorinated complexes show significantly different solvation properties from those of the analogous unfluorinated compounds, particularly with respect to their behavior in common organic solvents and their good scCO2 solubility.