Low molecular weight poly(2-hydroxyethyl methacrylate) (polyHEMA) with a number average molecular weight (Mn) <22,600, were prepared by atom transfer radical polymerization. The molecular weight and end groups of the polyHEMA were varied, and the water content equilibrium moisture sorption and water structure were analyzed using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Higher water content was observed for polyHEMA with Mn < 10,000. DSC revealed that the amounts of nonfreezing water are affected neither by the molecular weight nor by the end groups of the polyHEMA. On the other hand, the amount of freezing water was affected by both the molecular weight and end groups of polyHEMA, especially for polyHEMA with Mn < 20,000. The XRD-DSC measurements showed that water in polyHEMA form hexagonal ice and that the direction of crystal growth is dependent on the molecular weight. These findings indicate that the molecular weight of polyHEMA plays a significant role in the water structure in polyHEMA. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012