Hazardous Air Pollutants (HAPs) are present in low concentrations in the environmental air, but have the potential to cause serious harm to humans, animals, and plants through long-term exposure. HAPs have carcinogenic, genotoxic, organismal accumulation, and mutagenic properties. In this study, we conducted a monitoring study of gaseous HAPs pollutants volatile organic compounds (VOCs) in Yeosu-Gwangyang, Pohang, Daesan, Ulsan-Onsan, and Sihwa-Banwol industrial complexes and obtained the following results. The concentration of total VOCs in 5 industrial complexes are Sihwa · Banwol 84.58 μ/m3, Ulsan · Onsan 52.09 μ/m3, Pohang 46.24 μ/m3, Daesan 45.64 μ/m3, Yeosu · Gwangyang 38.51 μ/m3, in order, the Sihwa · Banwol industrial complexes showed the highest, and the Yeosu · Gwangyang industrial complexes showed the lowest. The concentration of benzene in all five industrial complexes was below environmental standards, and its concentration was 0.73 ppb in Yeosu-Gwangyang, 0.57 ppb in Pohang, 0.78 ppb in Daesan, 1.02 ppb in Ulsan-Onsan, and 0.51 ppb in Sihwa-Banwol. Among the VOCs, the highest average concentration is formaldehyde in Yeosu-Gwangyang, Pohang, Daesan, and Ulsan-Onsan, and acetone in Sihwa-Banwol. The toluene/benzene(T/B), m,p-Xylene/ethylbenzene (X/E) ratio and conditional probability function (CPF) model were used to evaluate the location of pollution sources at the measurement points.