Reversible addition-fragmentation chain transfer (RAFT) polymerization is a more robust and versatile approach than other living free radical polymerization methods, providing a reactive thiocarbonylthio end group. A series of well-defined star diblock [poly(e-caprolactone)-b-poly(N-isopropylacrylamide)]4 (SPCLNIP) copolymers were synthesized by R-RAFT polymerization of N-isopropylacrylamide (NIPAAm) using [PCL-DDAT]4 (SPCL-DDAT) as a star macro-RAFT agent (DDAT: S-1-dodecyl-S'-(a, a'-dimethyl-a?-acetic acid) trithiocarbonate). The R-RAFT polymerization showed a controlled/living character, proceeding with pseudo-first-order kinetics. All these star polymers with different molecular weights exhibited narrow molecular weight distributions of less than 1.2. The effect of polymerization temperature and molecular weight of the star macro-RAFT agent on the polymerization kinetics of NIPAAm monomers was also addressed. Hardly any radicalradical coupling by-products were detected, while linear side products were kept to a minimum by careful control over polymerization conditions. The trithiocarbonate groups were transferred to polymer chain ends by R-RAFT polymerization, providing potential possibility of further modification by thiocarbonylthio chemistry. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 571-580, 2012