The growing transportation risk of hazardous materials (hazmat) is an important threat to public safety. As an efficient and reliable mode of transportation, the multimodal hub-and-spoke transport network helps to achieve economies of scale and reduce costs. Considering the dual goals of risk and cost management of hazmat transportation, a novel optimization model of a multimodal hub-and-spoke network with detour (MHSNWD) for hazmat on the strategic level is designed. It integrates the planning of hub location and route selection based on the risk quantification for different transportation modes. Additionally, a detour strategy is applied, which allows for more than two hub nodes to be selected to form an optimal path between any supply and demand nodes in a hub-and-spoke network. Then, the risk is taken as the main objective and the cost is converted into a budget constraint to solve the model by using CPLEX. Additionally, a numerical study is conducted based on a CAB dataset to find the influence of the number of hubs and budget constraints on the optimization results. In addition, a counterpart model of the multimodal hub-and-spoke network without detour (MHSNOD) is tested to validate the advantages of the proposed model of MHSNWD. The numerical experiment shows that an appropriate increase in the number of hubs and the cost budget can remarkably reduce network risk. Compared with MHSNOD, the optimal result of MHSNWD can achieve a marginal improvement in risk reduction. This work may provide an informative decision-making reference for planning a hazmat transportation network.