With economic growth, the use of chemicals has continually increased, resulting in an increase of chemical accidents. Chemical accidents pose a life threat and can lead to many health problems among the residents living in close proximity to chemical plants. This study aimed to investigate the awareness of the residents living near chemical plants about hazardous chemicals, as well as to survey the awareness of workers who do not directly handle chemicals at chemical plants (WNHCs). To this end, a questionnaire survey was conducted among a total of 600 residents and 160 WNHCs. The questionnaire was composed of three items: awareness of chemical risk, awareness of countermeasures in chemical accidents, and imperious necessity of PPE (personal protective equipment). Statistical analysis of the data was performed with the Statistical Package for Social Sciences (SPSS) version 18.0. The results show that the government needs to complement the notification system of chemical risk for residents who live close to chemical plants. The highest priority of PPE which residents want to prepare for chemical accidents was respiratory protective equipment (RPE). They responded that, if necessary to purchase PPE, they could bear a portion of the expenses (up to US $30). This study provides basic data for the development of programs and policies on chemical safety relevant for the residents living in close proximity to chemical plants in South Korea.