The novel core-shell polymers were synthesized based on the perfluoroalkyls grafting onto the inner hydroxyl groups of hyperbranched polyglycidol while the outer hydroxyl groups remained unaffected. The samples were characterized with FTIR, NMR, element analysis, and liquid chromatography/mass spectrometry. The various results obtained by different measurements are in good agreements. The conversion ratio of inner hydroxyl groups is about 0.3 and most functionalizations took place in linear 1,4-units (L1-4). Differential Scanning Calorimetry results suggest the samples are amorphous within the experiment range. Their inner lipophilicity and outer hydrophilism resulted from their unique structures are expected to gain promising applications. (c) 2006 Wiley Periodicals, Inc.