The versatile chloromethyl TIPNO-based alkoxyamine was efficiently transformed into other valuable functionalised TIPNO-based alkoxyamines such as amino alkoxyamines which are interesting initiators for block copolymers and bisalkoxyamines in good yield and in two steps at the most. One bisalkoxyamine has allowed to prepare well-defined polystyrene-b-poly(n-butyl acrylate)-b-polystyrene symmetrical triblock copolymer. The last representative example of such alkoxyamines is a styrenic alkoxyamine which was copolymerized with styrene to afford branched polystyrene. Finally, for the first time branched poly(n-butyl acrylate) by nitroxide mediated radical polymerization was obtained and was a efficient macroinitiator of styrene, which indicates that the radical polymerization mediated by this styrenic alkoxyamine is living. (C) 2009 Elsevier Ltd. All rights reserved.