Two new CO2-soluble rhenium(I) bipyridine complexes bearing the fluorinated alkyl ligands 4,4'-(C6F13CH2CH2CH2)(2)-2,2'-bipyridine (1a), and 4,4'-(C8F17CH2CH2CH2)(2)-2,2'-bipyridine (1b) have been prepared and their photophysical properties investigated in CH3CN and supercritical CO2. Electrochemical and spectroscopic characterization of these complexes in CH3CN suggests that the three methylene units effectively insulate the bipyridyl rings and the rhenium center from the electron-withdrawing effect of the fluorinated alkyl chains. Reductive quenching of the metal-to-ligand charge-transter excited states with triethylamine reveals quenching rate constants in supercritical CO2 that are only 6 times slower than those in CH3CN.