Well-defined D-glucose-containing glycopolymers, poly(3-O-methaeryloyl-1,2: 5,6-di-O-isopropylidene-D-glucofuranose) (PMAIpGlc), and diblock copolymers of PMAIpGlc with poly(1,1-dihydroperfluorooctyl methacrylate) (PFOMA) were synthesized by living anionic polymerization in THF at -78 degreesC with 1, 1-diphenylhexyllithium in the presence of lithium chloride. The resulting polymers were found to possess predictable molecular weights and very narrow molecular weight distributions (MWD, M-w/M-n less than or equal to 1.16). Removal of the acetal protective groups from the protected glycopolymer block copolymer was carried out using 90% trifluoroacetic acid at room temperature, yielding a hydrophilic block copolymer with pendant glucose moieties. Both protected (lipophilic/CO2-philic) and deprotected (hydrophilic/CO2-philic) fluorocopolymers were proved to be CO2 amphiphiles. Their solubility in CO2 was heavily influenced by the amphiphilic structure, such as the copolymer compositions and the polarities of sugar block. Light-scattering studies showed that, after removal of the protective groups, the deprotected block copolymer formed aggregate structures in liquid CO2 with an average micellar size of 27 nm.