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Well defined graft copolymers have been synthesized by a nitroxide‐mediated “living” free radical process using pre‐formed macromonomers. Analysis of the graft systems revealed that the macromonomer was efficiently incorporated into the polymeric backbone to give block copolymers of controlled molecular weight and narrow polydispersities. An added benefit of the “living” free radical process is that macromonomers, such as polylactide or polycaprolactone, which contain reactive functional groups can be used to form novel graft systems using this approach. Functionalized monomers or polymeric initiators were also used in the copolymerization mixture to give graft systems with a variety of functional groups attached to the backbone.