Many materials which are important for a sustainable society are hazardous materials (hazmat), and there is the risk of potential threats with undesirable impacts on the sustainability of transport systems. The goal of this study is the mitigation of sustainability risks associated with hazmat transport processes. Moreover, it is necessary to design reliable road hazmat transport networks based on risk mitigation. This research combines route planning of hazmat shipments with location for emergency response centers in a road hazmat transport network. In addition, a new subsidy policy is also proposed. Hazmat carriers are able to choose routes for shipments in accordance with minimum transport costs. As a game scenario, a bi-level programming model is established to describe the problem. A genetic algorithm is developed to solve the problem, and computational experiments are made to testify the effectiveness of the proposed method. The results show the reasonableness of the model and the effectiveness of the algorithm, calibrating the influence of the parameters and the optimization characteristics of certain practical scenarios. Overall, the purpose of this paper is to develop a complete optimization approach for the design of road hazmat transport networks with sustainable risk as the key innovation.