Compatibility of starch/polyvinyl alcohol (PVA) blends, prepared by solution cast method, is dependent on the blend composition. Crystallinity of the blend, as measured by X-ray diffraction (XRD) and differential scanning calorimeter (DSC), decreases with increase in starch content. Thermogravimetric analysis (TGA) shows that the broadness in the peak width at the degradation region increases with increase in starch content in the starch/PVA blend. Dynamic mechanical thermal analysis (DMTA) reveal that the broadness of the relaxation peaks is due to the partial compatibility of the glycerol plasticized starch/PVA blends. The tensile property decreases with increase in starch content and the 30/70 starch/PVA blend shows maximum ductility in respect to both the percentage of elongation and energy at break. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers