Liquid and/or supercritical carbon dioxide as a useful processing fluid is limited by its inability to solubilize highly polar compounds. This problem can be alleviated by the addition of CO2-philic amphiphiles. Our primary objective herein is to design and synthesize novel materials that have both strong polar moieties and highly CO2-philic segments. Sugar-containing hydrophobic/hydrophilic fluorinated copolymers were synthesized by free-radical polymerization. The degree of solubility of the amphiphiles in CO2 was found to be heavily influenced by the amphiphilic structure, including the polarity of the sugar head (acetal protected and deprotected), and the fraction of CO2-philic groups. We also found that the presence of water in the CO2 phase could decrease the solubility of the hydrophilic copolymer. The dispersion polymerization of 2-hydroxyethyl methacrylate in CO2 was tested by using the hydrophilic amphiphile as a stabilizer. Spherical particles in the submicron size range were obtained.