Abstract: With the globalization of the world economy and the deepen integration, China's relations with the world is deeper and deeper and China has entered a rapid development stage. Because of the special nature of hazardous chemicals, once the accident happened will lead to the more destructive accidents than the general ones, so it needs special attention, especially during the processing of transportation. Based on this background, this study will consider the modes of railway and highway, to establish the risk assessment model which is a bi-objective programming model considering the risk and cost and solved by matlab. In the end can get the conclusion: combined transport mode can reduce costs and achieve the purpose of avoiding risk; similarity, we need to choose reasonable transportation time to achieve the purpose of accurate delivery.