A L-valine-derived α-haloamide was synthesized and investigated as an initiator for the atom transfer radical polymerization of tert-butyl acrylate using commercially available CuBr, CuBr(2) and N,N,N',N",N"-pentamethyldiethylenetriamine as the catalyst and ligand system. Kinetic studies and extension to a diblock copolymer with styrene, each indicated that the polymerizations were well controlled. Poly(tert-butyl acrylate) having M(n) (NMR) = 8.6 kDa, M(n) (GPC) = 8.3 kDa, PDI = 1.11 and a diblock of poly(tert-butyl acrylate)-b-polystyrene having M(n) (NMR) = 20.2 kDa, M(n) (GPC) = 22.5 kDa, PDI = 1.22 were prepared by the sequential polymerization of tert-butyl acrylate and styrene at 55 °C and 90 °C, respectively.