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The transportation volume of hazardous material is increasing, and the potential risk of hazardous material for environment and mankind is enlarging. How to select the best transportation route, insure transportation safety and reach destination rapidly is an important problem for decision department. The transportation route decision-making method of hazardous material is put forward in this paper. A scientific and reasonable transportation route is the essential condition to ensure the hazardous material transportation safety. On the foundation of considering the factors which affecting the hazardous material safety, a new evaluation index system is set up, and a new evaluation model is established based on particle swarm optimization algorithm and BP neural networks. The example shows that the new evaluation index system is scientific and the new evaluation model is feasible. The decision making methods of hazardous material can help the government supervision and management department choose the best route.