Polymerization of 2-(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10-hexamethyl triethylenetetramine/copper(I) chloride/p-toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. 1. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well-defined block copolymers of DEAEMA and tert-butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well-defined copolymers. (C) 2003 Wiley Periodicals, Inc.