A novel amphiphilic ABA type triblock copolymer with well-defined glycopolymer segments was successfully synthesized via the atom transfer radical polymerization (ATRP) technique, using a bromo-terminated difunctional polysulfone as macroinitiator. The difunctional polysulfone macroinitiator was prepared by esterifying the phenolic end groups of polysulfone to α-haloesters. This macroinitiator was then used to initiate the polymerization of a glucose-carrying monomer, 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose (MAIpG), resulting an ABA type triblock copolymer. After acidolysis treatment, the isopropylidenyl groups of the protected sugar residues were removed, thus the amphiphilic ABA type triblock copolymer with well-defined glycopolymer segments was obtained. The polymers obtained were identified by FT-IR, 1H-NMR, GPC, and TGA. The self-assembly behavior of the amphiphilic glycopolymer in selective solvent (e.g. DMF/H2O) system was also preliminarily explored. The resultant amphiphilic glycopolymer shows potential applications in the fields of controlled release and delivery of drugs, micro-reactors, nano-materials, medical devices, and so on.