2,2,6,6-Tetramethyl-4-[d-(+)-10-camphorsulfonyl]-1-piperidinyloxy was synthesized and used as a chiral nitroxide for the bulk polymerizations of styrene initiated with benzoyl peroxide (BPO), tetraethylthiuram disulfide (TETD), and thermal initiation. The results showed that the polymerizations proceeded in a controlled/living way; that is, the kinetics presented approximately first-order plots, and the number-average molecular weights of the polymers with narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight) increased with the monomer conversion linearly. The molecular weight distributions in the case of thermal initiation were narrower than those in the case of BPO and TETD, whereas the polymerization rate with BPO or TETD as an initiator was obviously faster than that with thermal initiation. In addition, successful chain-extension reactions were carried out, and the structures of the obtained polymers were characterized by gel permeation chromatography and H-1 NMR. The specific rotations of the polymers were also measured by polarimetric analysis. (c) 2006 Wiley Periodicals, Inc.