Starch/poly(vinyl alcohol) (PVA) films were prepared with calcium chloride (CaCl 2 ) as the plasticizer. The micro morphology of pure starch/PVA film and CaCl 2 plasticized starch/PVA film was observed by scanning electron microscope. The interaction between CaCl 2 and starch/PVA molecules was investigated by Fourier transform infrared spectroscopy. The influence of CaCl 2 on the crystalline, thermal and mechanical properties of starch/PVA films was studied by X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and tensile testing, respectively. The results indicated that CaCl 2 could interact with starch and PVA molecules and then effectively destroy the crystals of starch and PVA. Starch/PVA films plasticized with CaCl 2 became soft and ductile, with lower tensile strength and higher elongation at break compared with pure starch/PVA film. The water content of starch/PVA film would increase with the addition of CaCl 2 . This is an important cause of the plasticization of CaCl 2 on starch/PVA film.