Hazardous chemicals are harmful to the people around them during their storage, especially when an accident occurs. The allocation and scheduling of emergency materials, therefore, is an important imperative of emergency rescue services. Due to the harmful characteristics of dangerous goods, the storage risk of hazardous chemicals in emergency networks always exists, which threatens surrounding residents. To reduce the risk of hazardous chemicals storage in terms of emergency networks, the collaborative optimization of emergency materials allocation and scheduling from the perspective of risk is proposed in the present study. The risk assessment of dangerous goods storage in different stages is developed. Minimizing the total cost and risk, a bi-level programming model of emergency material allocation and scheduling for dangerous goods storage is formulated. Then, the Karush–Kuhn–Tucker (KKT) condition is introduced to transform the proposed model, and the solution method is designed based on an augmented ε-constraint method. Finally, the computational case is provided to demonstrate the workability of the proposed model and method.