Radical polymerization of N-isopropylacrylamide (NIPAAm) was investigated at low temperatures in the presence of both hexamethylphosphoramide (HMPA) and alkyl alcohols. Although HMPA and alkyl alcohols separately induced syndiotactic specificity in NIPAAm polymerization in toluene at low temperatures, a combination of HMPA and less bulky alkyl alcohols, such as methanol and ethanol, was found to induce isotactic specificity at -80 degrees C. NMR analysis of mixtures of NIPAAm, ethanol and HMPA suggested the formation of a 1:1:1 complex through O-H center dot center dot center dot O=C and N-H center dot center dot center dot O=P hydrogen bonding. It is believed that the steric effect of HMPA enhanced by cooperative hydrogen bonding was responsible for the combined effect of HMPA and alkyl alcohols in inducing isotactic specificity. (C) 2010 Elsevier Ltd. All rights reserved.