Radical polymerization of N-isopropylacrylamide in toluene at -40 degrees C in the presence of fourfold amounts of fluorinated alcohols was investigated. The C-13 NMR analysis of the obtained polymers suggested that the addition of fluorinated alcohols induced heterotactic specificity in radical polymerization of NIPAAm, although syndiotactic poly(NIPAAm)s were obtained by adding alkyl alcohols as we have previously reported. To the best of our knowledge, this is the first synthesis of heterotactic poly(NIPAAm). (c) 2007 Elsevier Ltd. All rights reserved.