The risk assessment of thermal behavior and runaway reaction cased by an exothermic batch process in manufacture of the vinyl acetate resin are described in the present paper. The aim of the study was to evaluate the risk of runaway reaction with operating parameters such as a reaction inhibitor, reaction temperature and a mount of methanol charged in the vinyl acetate polymerization process. The experiments were performed by a sort of calorimetry with the Multimax reactor system as a screening tool to investigate runaway reaction. From the experimental results, it was found that we could occur the auto acceleration for reaction of raw materials with operating parameters over $65^{circ}C$ of reaction temperature in the vinyl acetate polymerization process.