Recently, hazardous chemical accidents have increased in Korea due to large amounts of chemicals used for industrial purposes and deterioration of individual facilities in national industrial complexes. However, there is no information on which chemicals and areas should be preferentially managed on a local scale. In this study, we developed a systematic method to select priority chemicals and areas for the response to chemical accidents in national industrial complexes. This method was applied to Ulsan as a case study. The priority chemicals (top 10%) in Ulsan were listed as xylenes, ethylbenzene, toluene, ethylene, benzene, methanol, ethylene oxide, and propylene. In addition, local areas of Yecheon, Joenha, and Gosa were expected as vulnerable areas for chemical accidents. The method developed in this study can be applied to other cities and used for chemical accident management systems by national and local authorities.