A one-step thermal extrusion process has been investigated for the modification of starch with alcohol in order to improve the film properties. Unmodified starch/glycerol mixtures containing Methanol,ethanol and their combinations (5,10,15 wt%) were thermally extruded to produce thermoplastic. The final hot-pressed film showed increased stiffness and crystallinity, while having decreased moisture uptake due to oxidation and alcohol complexing molecular interactions. The young's Modulus, tensile strength and elongation at break increased by 60%,15% and 32% respectively,for 5 wt% methanol derived film,compared to the control.The film moisture content was reduced by up to 15 wt% for 5 wt% ethanol -derived film.Generally the crystallinity increased in the alcohol-derived films due ti sn increased complexing of alcohol with starch forming the Vh ploymorph. Fourier transform infra-red and proton nuclear magnetic resonance spectroscopic analysis were used to discuss the milecular interactions between the starch and alcohol molecule