Radical polymerization of N-isopropylacrylamide (NIPAAm) in CHCl3 at low temperatures in the presence of pyridine N-oxide (PNO) was investigated. An isotactic poly(NIPAAm) with meso diad content of 61% was successfully prepared at -60 degrees C in the presence of a two-fold amount of PNO. Thermodynamic analysis suggested that the isotactic-specificity was entropically induced, probably due to conformational fixation near the propagating chain-end through coordination by PNO. (c) 2005 Elsevier Ltd. All rights reserved.