Starch is one of the most popular biodegradable polymers in nature, which is gaining increasing attention because of its abundant availability and low cost. However, starch film itself is very brittle and its barrier property is poor for many applications. Polyvinyl alcohol (PVA), a versatile polymer in paper industry, is used to improve the barrier property of starch film. In this study, painting paper with exceptional barrier properties against organic solvents is successfully prepared for art creation purpose by coating a thin layer of environmentally friendly starch/PVA film on its surface. The coated paper can resist the penetration of the ink from marker pens. Furthermore, the solvent resistance and mechanical flexibility of freestanding starch/PVA hybrid film were investigated in detail. It found that the excellent barrier properties of the coated painting paper against solvents are due to the superior solvent resistance and mechanical flexibility of starch/PVA hybrid film. Therefore, the biodegradable and cost-effective strategy in this study provides a promising approach to enhance the barrier property of painting paper against solvents, which can find potential applications in painting field.