In Taiwan, disaster prevention and fire rescue are handled by fire units. However, facing chemical factory fires, general fire branches have neither adequate protective equipment nor rescue skills. So far, the setting assessment of general fire branches is often based on statistical methods of the fire number, and focus on the casualties, losses and causes of disasters. But it can not indicate truly high-potential regional chemical fire areas, so that fire units have to mobilize all members in strategy which causes huge waste of manpower and resources and may not be effective. The selection of fire branches has a relationship with the time-effectiveness of fire rescue and the service scope. This study is based on the chemical fire cases that occurred in Tainan City in the recent 5 years (from 2013 to 2017), matched with the distribution of disaster rescue capacity, and via the survey and the experts (scholars) to produce important evaluation factors which add appropriate weight to the Analytic Hierarchy Process (AHP). By discussing the fire potential areas and the efficiency of fire branches, the Technique of Order Preference by Similarity to Ideal Solution (TOPSIS) is combined with the subjective urgency verification and the service scope of fire branches to get the best setting order of chemical disaster rescue teams, as a reference of fire prevention strategy and the fire branches selection in the future.