A series of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) analogue surfactants sodium dibutyl sulfosuccinate (DBSS), sodium dipentyl sulfosuccinate (DPSS), sodium dihexyl sulfosuccinate (DHSS), and sodium dioctyl sulfosuccinate (DOSS) were synthesized and characterized with 1H NMR and elemental analysis. The solubilities of surfactants in supercritical CO2(scCO2) and supercritical 1,1,1,2-tetrafluoroethane (HFC-134a) fluids at a temperature range from (308 to 338) K and under pressures of (10 to 30) MPa were measured using a static method coupled with gravimetric analysis. The solubilities of these surfactants are much higher in HFC-134a fluid as compared with that in scCO2. The solubilities increased with increasing temperature and pressure for both scCO2and HFC-134a fluids. The solubilities in scCO2increased with increasing carbon atom number of surfactant, whereas they decreased with increasing carbon atom number of surfactant in HFC-134a. The density of scCO2was simulated with the Peng−Robinson (P-R) equation. The experimental data were used to validate the accuracy of the P-R equation.