The radical polymerization of methylmethacrylate and ethylacrylate was carried out in the presence of tris(4,4＇-dimethyl-2,2＇-bipyridine) copper(II) hexafluorophosphate complexes and aluminium isopropoxide. The molecular weight of the synthesized polyethylacrylates increased proportionally with conversion, whereas the polymerization of methylmethacrylate revealed a nonlinear behavior. The polydispersities of the molecular weight distributions observed were between 1.09 and 1.34. Poly(styrene-block-polymethyl-methacrylate) was synthesized by sequential monomer addition.