Well-defined amphiphilic block-graft copolymers PCL-b-[DTC-co-(MTC-mPEG)] with polyethylene glycol methyl ether pendant chains were designed and synthesized. First, monohydroxyl-terminated macroinitiators PCL-OH were prepared. Then, ring-opening copolymerization of 2,2-dimethyltrimethylene carbonate (DTC) and cyclic carbonate-terminated PEG (MTC-mPEG) macromonomer was carried out in the presence of the macroinitiator in bulk to give the target copolymers. All the polymers were characterized by H-1 NMR and gel permeation chromatography (GPC). The polymers have unimodal molecular weight distributions and moderate polydispersity indexes. The amphiphilic block-graft copolymers self-assemble in water forming stable micelle solutions with a narrow size distribution.