This research studied human health risk assessment of benzene from industrial complexes of Chungcheong Province (Seosan industrial complex) and Jeonla Province (Iksan industrial complex and Yeosoo industrial complex). The residents near the industrial complexes areas can be often exposed to volatile organic compounds (e.g., benzene, toluene, xylenes) through a number of exposure pathways, including inhalation of the organic pollutant via various environmental matrices (air, water and soil), contaminated water, and soil intake. Benzene is well known to be a common carcinogenic and toxic compound that is produced from industrial and oil refinery complexes. In this study, a number of samples from water, air, and soil were taken from the residential settings and public school zones located near the industrial complex sites. Based on the carcinogenic risk assessment, the risk estimates were slightly above 1.0×10^(-6)at all three industrial sites. According to deterministic risk assessment, inhalation was the most important route. The distribution of benzene in the environment would be dependent on vapor pressure, and the physical property influencing the extent of the potential risks. Noncarcinogenic risk assessment of benzene shows that the values of Hazard Index(HI) were much lower than 1.0 at all industrial complexes. Therefore, benzene was not a cause of concern in terms of non-carcinogenic risk posed to the residents near the sites. When compared to probabilistic risk assessment, the CTE(central tendency exposure) cancer risk values of deterministic risk assessment were close to the mean values predicted by the probabilistic risk assessment. The RME(reasonable maximum exposure) values fell within the range of 95% to 99.9% estimated by the probabilistic risk assessment. Since the values of carcinogenic risk assessment were higher than 1.0×10^(-6), further detailed monitoring and refined risk assessment for benzene may be warranted to estimate more reliable and potential inhalation risks to receptors near the industrial complexes.