A series of gelatinized polyvinyl alcohol (PVA):starch blends were prepared with various polyol-based plasticizers in 5 wt%, 15 wt% and 25 wt% ratios via solution casting method. The obtained films were analyzed by Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Remarkable changes have been observed in glass-transition temperature (T-g) and thermal stability of the samples containing varying concentrations of different plasticizers and they have been discussed in detail with respect to the conducted thermal and chemical analyses. The observed order of Tg point depression of the samples containing 15 wt% plasticizer is 1,4-butanediol - 1,2,6-hexanetriol - pentaerythriyol - xylitol - mannitol, which is similar to the sequence of the thermal stability changes of the samples. (C) 2015 Elsevier Ltd. All rights reserved.