The synthesis of polymers with well-defined compositions, architectures, and functionalities has long been of great interest in polymer chemistry. Typically, living polymerization techniques are employed where the polymerizations proceed in the absence of irreversible chain transfer and chain termination. 1-3 Much of the academic and industrial research on living polymerization has focused on anionic, cationic, coordination, and ring-opening polymerizations. The development of controlled/living radical polymerization (CRP) methods has been a long-standing goal in polymer chemistry, as a radical process is more tolerant of functional groups and impurities and is the leading industrial method to produce polymers. 4 Despite its tremendous industrial utility, CRP has not been realized until recently, largely due to the inevitable, near diffusion-controlled bimolecular radical coupling and disproportionation reactions.