Functionalized poly(ethylene oxide) (PEO) macromonomers (alpha -tertiary amino and omega -methacryloyl groups) were prepared by ring-opening polymerization of living PEO anions using 2-[2-(N,N-dimethylamino)-ethoxy]ethanol potassium alkoxides as an initiator with glycidyl methacrylate. Terminal double bond functionality was controlled in the range of 1-1.5 per molecule in toluene as the hydrocarbon solvent. However, gelation was observed upon such ring-opening polymerization system in tetrahydrofuran solvent. These macromonomers can be applied for the synthesis of peripheral functionalized stars and polymer brushes as the starting materials.