A series of multihydroxyl (2, 4, and 8) terminated poly(ethylene glycol)s and their biodegradable, biocompatible, and branched barbell-like (PLGA)(n)-b-PEG-b-(PLGA)(n) (n = 1, 2, 4) copolymers have been synthesized. The lengths of the PLGA arms were varied by controlling the molar ratio of monomers to hydroxyl groups of PEG ([LA+GA](0)/[-OH](0) = 23, 45, 90). Chemical structures of synthesized barbell-like copolymers were confirmed by both H-1 and C-13-NMR spectroscopies. Molecular weights were determined by H-1-NMR end-group analysis and gel permeation chromatography. The result of hydrolytic degradation indicated that the rate of degradation increased with the increase of arm numbers or with the decrease of arm lengths. The thermal properties were evaluated by using differential scanning calorimetry and a thermogravimetric analysis. The results indicated that the thermal properties of barbell-like copolymers depended on the structural variations. The morphology of (PLGA)(n)-PEG-(PLGA)(n) copolymers self-assembly films were investigated by atomic force microscope, the results indicated that the microphase separation existed in (PLGA)(n)-PEG-(PLGA)(n) copolymers. Because of the favorable biodegradability and biocompatibility of the PLGA and PEG, these results may therefore create new possibilities for these novel structural amphiphilic barbell-like copolymers as potential biomaterials. (C) 2008 Wiley Periodicals, Inc.