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The classification of early warning and response of Highway Traffic Emergency (HTE) is the foundation of the solution to THE, as it is directly bound up with the responders, the available measures and resources. Firstly, this paper discusses three major factors that affect the classification to early warning and response of HTE: affected area, classes and property of highway, duration time. Based on factors analysis, scores are assigned for each factor through decision theory, and further the weight of each factor is determined through expert scoring and Analytical Hierarchy Process (AHP) method. After that, this paper is to establish classification function, and to define the range of scores for each class. Finally, this paper is to conduct a case study of accident of “3.29” liquid chlorine leaking at Jing-hu expressway, to prove the validity of the method.