The work aims to prepare the blending film with whole corn flour and polyvinyl alcohol (PVA) and study its performance structure, expecting to replace the traditional plastic packaging bags to alleviate the harm caused by white pollution. The whole corn flour/PVA blending films were prepared in solution casting method with triethanolamine and carboxymethylcellulose. The influence of PVA content on mechanical properties, hygroscopicity and water vapor transmission rate of blending films were studied. The results showed that tensile strength, elongation at break and tear strength of blending films strengthened and the moisture absorption and water vapor transmission rate decreased with the increase of PVA content. The mechanical properties of blending films declined after moisture absorption. Microscopic observation indicated that the increase of PVA content could improve the compatibility of the blending system. The blending film containing 40%~60% (mass fraction) PVA in the raw material substrate had a tensile strength of above 10 MPa, moisture absorption of below 82% and water vapor transmission rate of about 12×10−5 g/(mm•d). The blending films have certain ability to resist the water vapor and oil permeability, which can basically meet the requirements of ordinary packaging materials.