N-Isopropyl-4-vinylbenzylamine (PVBA) was synthesized and used as an initiator for the polymerization of methacrylates to synthesize macromonomers with terminal styrenic moieties. LiPVBA initiated a living polymerization and block copolymerization of methyl methacrylate, 2-(NN-dimethylamino)ethyl methacrylate and tert-butyl methacrylate and produced polymers having well-controlled molecular weights and very low polydispersities ((M) over bar (w)/(M) over bar (n) < 1.1) in quantitative yield. H-1 NMR analysis revealed that the polymers contained terminal 4-vinylbenzyl groups. The macromonomers were reactive in the copolymerization with styrene.