The dimethylketals of poly(vinyl alcohol), termed polyvinylacetone (PVKA), of moderate ketalization degree in the range from 0.28 to 0.6 exhibited temperature-induced phase transition in aqueous solution, as revealed by cloud point measurements and electron micrographs, which was then further investigated on molecular level using solution-state H-1 NMR measurements. The present phase transition is caused by the amphiphilic characteristics in the polymer chain. Moreover, this finding could be further applied as a novel strategy in the syntheses of thermosensitive polymer by the hydrophobic functionalities of linear polyol. (c) 2006 Elsevier B.V. All rights reserved.