Melt blends of poly(ethylene oxide) (PEO) and poly(vinyl acetate (PVAc) were prepared andstudied by Torsional Pendulum Analysis (TPA) and Fourier Transform Infrared (FTIR). Two glasstransitions were found in these blends. The lower Tg corresponds to the segmental motion in thepure PEO. The dependence of the position and broadness of the higher Tg on composition of theblends indicates that the two components are compatible in the amorphous phase with micro-hetero-geneity. These Tg values observed from mixed PVAc/PEO phase are much higher than that calculated from Fox equation.The comparison of the blends quenched and annealed from melt implies that PVAc mixed with PEO at the segmental level on molten state and the deviation of Tg values from Fox equation could be due to variation of the blend's composition by crustallization of part of the PEO component.Further indication that the blends are compatible down to the level of chain segments and that there are specific interactions between PVAc and PEO molecules comes from the analysis of FTIR spectra of the blends and the solution of PVAc in diethylene glycol dimethyl ether.