The ability of different alkoxyamines (11, 12, 13, 14, and 15) to initiate controlled radical polymerization of styrene was evaluated. Among them, 2-hydroxymethyl-2- [(2-methyl-1-phenyl-propyl)-(1-phenyl-ethoxy)-amino]-propane-1,3-diol (15) gave the highest polymerization rate of styrene, and the best control over the molecular weight and the molecular weight distribution of polystyrene. Kinetic studies confirmed that with initiator 15 the polymerization of styrene proceeded in a controlled way. The controlled radical homopolymerization of multifunctional acryl- and methacryl derivatives using initiator 15 could not be realized as demonstrated by the high polydispersities (PD) obtained. However, it was possible to polymerize multifunctional acryl- and methacryl derivatives using a polystyrene macroinitiator (Pst) and, thus, novel amphiphilic block copolymers with a narrow molecular weight distribution were obtained. (c) 2005 Wiley Periodicals, Inc.