According to the object-oriented analysis method, the demand analysis of intelligent monitoring system for hazardous chemicals logistics based on RFID and WSN is carried out, which analyzes the essential use cases of the system, the performance requirements for system design and other requirements. Also, the functional framework and module of the software system and the logical frame of the hardware system are constructed. The composition and structure and the internal logical relationship are introduced; the intelligent decision-making function module is introduced and the overall structure is given, which highlights the key role and composition of the model base and analyzes the core issues of the intelligent decision-making of hazardous chemicals logistics. The warehouse distribution method of hazardous chemicals based on rolling time domain optimization strategy is studied. Considering the drive of the uncertainty of transportation process and arrival time and for the warehouse storage capacity, the storage and distribution model of hazardous chemicals is established based on rolling time domain optimization strategy with the goal of maximizing warehouse utilization efficiency under the constraints of the limited storage conditions of hazardous chemicals, storage capacity of the target warehouse, external environment of the warehouse, warehousing and transportation conditions to solve the problem identification of target warehouse and the distribution of storage capacity in the storage and distribution of hazardous chemicals.