The synthesis of the new a-hydrogen beating nitroxide, 2,2,5-trimethyl-4-(isopropyl)-3-azahexane-3-oxyl (BIPNO) (4), and its corresponding alkoxyamine, N-tertbutyl-N-(1-isopropyl-2-methyl-propyl)-O-(1-phenyl-ethyl)hydroxylam ine (PhEt-BIPNO) (7), are described in this paper. Reaction of styrene with the new nitroxide in the presence of a Jacobsen-like manganese catalyst, Mn(salen)Cl, at ambient atmosphere afforded the alkoxyamine in 96% yield. Styrene and n-butyl acrylate were polymerized in bulk in the presence of the new alkoxyamine. The alkoxyamine turned out to be a suitable "initiator" for controlled radical polymerization.