Carbon dioxide (CO2) at the subcritical, near-critical, and supercritical states has been found to be a powerful solvent with tunable characteristics. It is currently considered an alternative solvent to the conventional organic solvents and has attracted numerous industrial activities (processes). However, CO2 has been limited in its application due to challenges with dissolving polar macromolecules, which limits its applications. This article presents the solubilization of surfactant; octylphenol ethylene oxide (TX-100) and poly(ethylene glycol)-block-poly (propylene glycol)-block-poly (ethylene glycol) (PEG-PPG-PEG) in liquid carbon dioxide. The TX-100 is solubilized in the liquid CO2 in a programmable phase equilibrium analyzer at varying temperatures and pressures. The emulsion characteristics as well as the water capacity of TX-100 and PEG-PPGPEG each in liquid CO2 is predicted by using ethyl acetate as substituted solvent. For PEG-PPG-PEG and TX-100 emulsion systems, microemulsion form at water-to-surfactant volume ratios of less than 1.0 and 1.2 with their corresponding liquid CO2 volume of greater or equal to 94% and 94.6%, respectively.