The polymerization by ATRP of hydroxy and amino functional acrylates and methacrylates with tert-butyidimethylsilyl (TBDMS) or tertbutyloxycarbonyl (BOC) protective groups has been studied for the first time achieving high control over molecular weight and polydispersity. Detailed investigation of the ATRP of 2- ([tert-butyl(dimethyl)silyl]oxy)ethyl acrylate (M2b) in bulk and 2+tertbutoxycarbonyl)amino]ethyl 2-methylacrylate (M3a) in diphenyl ether (DPE) showed that the type of ligand plays an important role on either the polymerization rate or the degree of control of the polymerization. Among the ligands used, N,N,N,'N '' N ''-pentamethyI diethylenetriamine (PMDETA) was the most suitable ligand for ATRP of all functional acrylates and methacrylates. The kinetics of M2b and M3a polymerization using PMDETA as a ligand was reported and proved the living character of the polymerization. Well-defined block copolymers based on a halogen terminated polystyrene (Pst) macroinitiator and the functional acrylate and methacrylate monomers were successfully synthesized by ATRP, and subsequent deprotection of the protective groups from the acrylate or methacrylate segment afforded amphiphilic block copolymers with a specific solubility behavior. (c) 2005 Elsevier Ltd. All rights reserved.