Biocompatible and biodegradable synthetic materials have attracted considerable attention during the past two decades. In this work, a series of amphiphilic triblock copolymers containing D-galactopyranose were synthesized by atom transfer radical polymerization (ATRP). The macroinitiator was prepared by the esterification between poly(ethylene glycol) monomethyl ether with a number-average molecular weight of 1200 g/mol (MeOPEO-1200) and 2-bromoisobutyryl bromide. The sugar-bearing monomer, 6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-D-galactopyranose (MAIPG) was polymerized using PMDETA/CuBr as catalytic system and anisol as solvent. The chemical structure and composition of the resultant polymer MeOPEO-b-PMAIPG were verified by 1H NMR. The molecular weights and their polydispersities were characterized by gel permeation chromatography (GPC). The results indicate that the polymerization follows the mechanism of ATRP. The amphiphilic copolymers can self-assembly to from micelles with PMAIPG as the core and PEO as the corona, which have potential applications as biomaterials or controlled release drug delivery systems.