In this paper, the combination of atom transfer radical polymerization (ATRP) of 1-ethoxyethyl acrylate (EEA) and the copper(I) catalyzed "click" 1,3-dipolar cycloaddition reaction of azides and terminal alkynes was evaluated as a method to synthesize diverse amphiphilic copolymer structures. Using the 1-ethoxyethyl protecting group strategy, the application field was broadened with the synthesis of complex polymer structures containing poly(acrylic acid) (PAA) segments. A modular approach has been used: polymers with alkyne functionalities as well as azide functionalities have been synthesized. These polymers were subsequently "clicked" together to yield block copolymers. Furthermore, graft copolymers were synthesized by grafting alkyne-containing polymers onto a polymer backbone with multiple azide functions using the combination of ATRP and "click" reactions. (c) 2007 Elsevier Ltd. All rights reserved.