To improve the drawability of poly(vinyl alcohol) (PVA) thermal products, poly(ethylene oxide) (PEO), a special resin with good flexibility, excellent lubricity, and compatibility with many resins, was applied, and the Fourier transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WXRD) were adopted to study the hydrogen bonds, water states, thermal properties, crystal structure, and noniso-thermal crystallization of modified PVA. It was found that PEO formed strong hydrogen bonds with water and PVA, thus weakened the intra- and inter-hydrogen bonds of PVA, changed the aggregation states of PVA chains, and decreased its melting point and crystallinity. Moreover, the interactions among PVA, water, and PEO retarded the water evaporation and made more water remain in the system to plasticize PVA. The existence of PEO also slowed down the melt crystallization process of PVA, however, increased the nucleation points of system, thus made more and smaller spherulites formed. The weakened crystallization capability of PVA and the lubrication of PEO made PVA chains to have more mobility under the outside force and obtain high mechanical properties. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1946-1954, 2010