Carbon dioxide (CO 2 ) 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, CO 2 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 TM ) and poly(ethylene glycol)-block-poly (propylene glycol)-block-poly (ethylene glycol) (PEG-PPG-PEG) in liquid carbon dioxide. The TX-100 TM is solubilized in the liquid CO 2 in a programmable phase equilibrium analyzer at varying temperatures and pressures. The emulsion characteristics as well as the water capacity of TX-100 TM and PEG-PPGPEG each in liquid CO 2 is predicted by using ethyl acetate as substituted solvent. For PEG-PPG-PEG and TX-100 TM emulsion systems, microemulsion form at water-to-surfactant volume ratios of less than 1.0 and 1.2 with their corresponding liquid CO 2 volume of greater or equal to 94% and 94.6%, respectively.