The fluorinated double-tailed glutarate anionic surfactant, sodium 1,5-bis[(1H,1H,2H,2H-perfluorodecyl)oxy]-1,5-dioxopentane-2-sulfonate (8FG(EO)(2)), was found to stabilize water-in-supercritical CO(2) microemulsions with high water-to-surfactant molar ratios (W(0)). Studies were carried out here to obtain detailed information on the phase stability and nanostructure of the microemulsions by using a high-pressure UV-vis dye probe and small-angle neutron scattering (SANS) measurements. The UV-vis spectra, with methyl orange as a reporter dye, indicated a maximum attainable W(0) of 60 at 45 and 75 °C, and SANS profiles indicated regular droplet swelling with a linear relationship between the water core nanodroplet radius and W(0). This represents the highest water solubilization reported to date for any water-in-CO(2) microemulsion. Further analysis of the SANS data indicated critical packing parameters for 8FG(EO)(2) at the microemulsion interface >1.34, representing approximately 1.1 times the value for common aerosol-OT in water-in-heptane microemulsions under equivalent conditions.