The vinyl of the ester group of 2-vinyloxyethyl methacrylate was first selectively reacted with acetic acid to obtain 2-[1-(acetoxy) ethoxy] ethyl methacrylate (2). This protected monomer was subjected to anionic polymerization in tetrahydrofuran at -60 degrees C in the presence of LiCl, using 1,1-diphenylhexyllithium as initiator. The molecular weight of the polymer could thus be controlled and a narrow molecular weight distribution obtained. The protecting group, 1-(acetoxy)ethyl, could be easily eliminated (by quenching the polymerization reaction with methanol and water) to generate poly(a-hydroxyethyl methacrylate) (poly(HEMA)). Block copolymers were also prepared by the sequential anionic polymerization of MMA and 2 or styrene and 2. They possess narrow molecular weight distributions, and controlled molecular weights and compositions.