The synthetic methodologies for various well-defined chain-end-and in-chain-functionalized polystyrenes with a definite number Of D-glucose and/or D-galactose residues have been described. They are based on diverse modes of addition reactions of polystyryllithium with substituted 1,1-diphenylethylene derivatives with acetal-protected alpha -D-glucofuranose and alpha -D-galactopyranose residues, followed by deprotection. By employing these methodologies, chain-end-functionalized polystyrenes with 4, 6, and 8 D-glucose and/or D-galactose residues and in-chain-functionalized polystyrenes with 2, 4, 8, and 12 D-glucose residues were synthesized. These polymers all were precisely controlled with regard to molecular weight, molecular weight distribution, degree of functionalization, and functionalized position in a chain, Such functionalized polymers with monosaccharide residues aggregated possibly to form reversed micelles in cyclohexane at 39 degreesC. It was observed that the aggregation number increased as increasing with the number of monosaccharide residue of both chain-end-and in-chain-functionalized polymers.