A series of Aerosol-OT (AOT, sodium bis(2-ethylhexyl)sulfosuccinate) analogue fluorinated surfactants, i.e.,the sodium salt of bis(2,2,3,3,3-pentafluoropropyl) 2-sulfosuccinate (di-CF2), the sodium salt of bis(2,2,3,4,4,4-hexafluorobutyl)2-sulfosuccinate (di-HCF3), the sodium salt of bis(3,3,4,4,5,5,6,6,6-nonafluorohexyl)2-sulfosuccinate (di-HCF4), and the sodium salt of bis(2,2,3,3-tetrafluoropropyl) 2-sulfosuccinate (di-HCF2), were synthesized and characterized by 1H NMR, 13C NMR, 19F NMR, melting point, and elemental analysis. The pressure-temperature (P-T) phase diagrams for water-in-CO2 (W/CO2) and water-in-1,1,1,2-tetrafluoroethane (W/HFC-134a) microemulsions stabilized by the surfactants were determined. In this work, the phase behaviors for different surfactants are obtained in supercritical CO2 (scCO2) and 1,1,1,2-tetrafluoroethane (HFC-134a) as a function of temperature, pressure, and water-to-surfactant ratio. At a fixed temperature, the cloud-point pressures increased with the increase of water-to-surfactant ratio (Wo) and the concentration of the surfactants. The cloud-point pressures for the surfactants in HFC-134a decrease with an increase in temperature at a fixed Wo and a surfactant concentration, which is in opposition to the results obtained in scCO2.