We report the application of reversible addition-fragmentation chain transfer polymerization using a novel chain transfer agent toward the synthesis of a variety of copolymers containing proline-derived monomeric units. This methodology enables ready access to a number of polymeric species with narrow molecular weight distributions, reliable functional unit incorporations, and high conversions. The methodology is also a facile approach to novel copolymeric species incorporating amino, acids, which possess unique material properties and the potential for further organocatalytic application. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:6814-6826, 2009