The interaction between poly(vinyl alcohol) (PVA) and low-molar-weight poly(ethylene oxide) (PEG) was studied. The thermal stability, glass transition temperature (Tg), crystallization, and melting behaviors were characterized as functions of content and molar mass of PEG. Dynamic mechanical thermal analysis revealed that PEG was compatible with PVA and provided plasticization effect to the latter. However, the plasticization was countered by the formation of hydrogen bonds between PEG molecules and PVA segments, which depressed the movement of PVA segments. At moderate contents of PEG, the hydrogen bonds were responsible for the increase in Tg, increase in crystallization heat, and decrease in crystallization rate. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012