An improved atom transfer radical polymerization (ATRP) process was developed for use in a waterborne miniemulsion system. To conduct a successful ATRP in a heterogeneous waterborne system, it is of great importance to ensure control over the polymerization process while preserving colloidal stability. Efforts devoted to optimization of reaction conditions and improvement in the overall productivity of the process allowed the development of a novel, practical initiation system for ATRP suitable for use in a miniemulsion procedure that can provide copolymers of well-defined composition (e.g., block copolymers) and topologies (e.g., multiarm polymer). (C) 2003 Wiley Periodicals, Inc.