Starch plasticized with glycerol and blended with polyvinyl alcohol (PVA) is recommended for use as a biodegradable material. The present article reports the results of studies of the natural weather ageing of starch/PVA blends having various amounts of glycerol in natural weather conditions of Saudi Arabia, with special reference to morphology and thermal behavior. Neat PVA has been used as a control to understand its behavior in its blend with starch. Differential scanning calorimeter studies indicated that an increase in the exposure time of samples to natural environment increases the crystallinity of PVA due to the breakage of intermolecular hydrogen bonding, thus facilitating the removal of the amorphous portion of the polymers in the blend. Thermogravimetric analysis revealed that an increase in glycerol content enhanced the degradation of the polymer, which is corroborated with the findings from the surface morphology using scanning electron microscopy and Fourier transfer infrared spectroscopy analyses.