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The paper reports the results of studies on the effect of glycerol content on thermal, mechanical, and dynamic mechanical properties of blends of starch and polyvinyl alcohol (PVA). Degree of crystallinity of the starch/ PVA blends (4 g/4 g ratio) remains almost constant up to 3.78 g of glycerol as determined by differential scanning calorimetry (DSC) and x-ray diffraction studies. At higher loading of glycerol the crystallinity decreases. DTG thermograms revealed occurring of one maximum degradation temperature closer to that of starch in blends containing up to 3.78 g of glycerol. At higher glycerol content there gradually occur two distinct peaks of maximum degradation temperature, one occurring close to that of starch and other occurring close to the PVA peak, indicating phase separation of the blend components. Results of stress-strain studies indicate lowering of tensile properties and energy at break particularly at higher glycerol content (beyond 3.78 g). Dynamic mechanical studies reveal a sharp drop in dynamic modulus at higher glycerol content at all temperatures. The blend with low glycerol content shows transitions of starch, while the blend containing high glycerol content beyond 3.78 g display the transitions due to both starch and PVA.