The synthesis of new 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) styryl derivatives as mediators for the living free-radical polymerization is described. Two of the alpha-methyl groups at the 2- and 6-position of the parent TEMPO styryl alkoxyamine have been replaced by hydroxymethyl and silyloxymethyl groups. To further increase the steric hindrance around the alkoxyamine oxygen atom, the remaining two methyl groups have been substituted with larger ethyl groups. Styrene polymerizations using hydroxy-substituted TEMPO derivatives are fast, but are not well-controlled. As previously shown for other OH-substituted alkoxyamines, intramolecular H-bonding leads to an acceleration of the C-O bond homolysis and, hence, to an acceleration of the polymerization process. However, the OH groups also increase the alkoxyamine decomposition rate constant. The kinetics of the C-O bond homolysis have been determined using EPR spectroscopy. Decomposition studies have been conducted with the aid of H-1 NMR spectroscopy. In contrast to the OH-substituted alkoxyamines, highly hindered silyloxy-substituted TEMPO alkoxyamines turned out to be excellent mediator/initiators for the controlled styrene polymerization. Polystyrene with M-n of up to 80 000 g/mol and narrow polydispersities (PDI) has been prepared using the new alkoxyamines. Reactions have been conducted at 105 degreesC; however, even at 90 degreesC controlled but slow polymerizations can be achieved. Furthermore, and more importantly, poly(n-butyl acrylates) with narrow PDIs (<1.15) have been prepared at 105 degreesC with the new alkoxyamines. Controlled acrylate polymerization can be conducted at temperatures as low as 90 degreesC. The silylated alkoxyamines presented belong to the most efficient initiator/ mediators for the controlled acrylate polymerization known to date. The effect of the addition of free nitroxide on the acrylate polymerization is discussed. Moreover, the synthesis of diblock copolymers with narrow PDIs is described.