The industrial complexes built during the course of economic development in South Korea played a pivotal role in the country’s rapid economic growth. However, this growth was accompanied by health problems due to the pollutants released from the industrial complexes inevitably located near residential areas, given the limited land area available in South Korea. This study was conducted to evaluate the exposure to each pollutant emanating from industrial complexes for residents living in nearby areas, and to determine the substances requiring priority attention in future surveys. Pollutants were comprehensively categorized according to their emission and exposure levels based on data previously collected from the study areas. The emission, ambient concentration, and biomarker concentration levels of major pollutants emitted from eight national industrial complexes (Ulsan, Pohang, Gwangyang, Yeosu, Chungju, Daesan, Sihwa, and Banwol) were determined and tabulated. Each of the values was compared with the national/local average values, reference values, or control area concentrations depending on availability. Substances with completed exposure pathways and with high values for emissions, ambient concentrations, and biomarker concentrations were considered the substances posing exposure risks to the residents living near the corresponding industrial complex. The substances requiring continuous monitoring or supplementary exposure investigation were also categorized and presented. Lead and benzene had higher values for emissions, ambient concentrations, and biomarker concentrations in the Ulsan Industrial Complex area; thus, they were most likely to pose exposure risks to residents living in the area’s neighborhoods. In other areas, styrene, xylene, cadmium, nitrogen oxide, trichloroethylene, nickel, manganese, and chromium required continuous monitoring, and arsenic, nickel, manganese, and chromium required biomarker measurements. In conclusion, the substances identified and categorized in this study need to be given appropriate attention in future surveys on exposure risks and health effects related to industrial complexes.