This study aimed to evaluate the human health risks of volatile organic compounds (VOCs)in ambient air in the areas near industrial complexes in Daesan, Ulsan, and Yeosu. Using data of hazardous air pollutant measurement network from the National Institute of Environmental Research(NIER) from 2021 to 2023, we analyzed the concentration distribution of VOCs and evaluated theirnon-carcinogenic and carcinogenic risks. The results of VOCs analysis for each industrial complexshowed that the total concentration of VOCs is trending upward in all industrial complexes, and themain substances contributing to the increase in concentration are 1,3-butadiene, 1,2-dichloroethane(Daesan), toluene and xylene(Ulsan, Yeosu). The non-carcinogenic risk assessment revealed that thehazard index (HI) value was less than 1 at all sites, indicating that no significant non-carcinogenic risksfrom exposure of airborne VOCs may occur nearby at the sites. However, the carcinogenic riskassessment indicated that the excess carcinogenic risk (ECR) of 1,3-butadiene and 1,2-dichloroethanewas more than the acceptable risk level (1.0×10-6) at Daesan Industrial Complex, while 1,3-butadieneexceeded the risk level at Ulsan and Yeosu Industrial Complexes. By conducting the probabilistic riskassessment for these substances, the acceptable risk levels (1.0×10-6) of 1,3-butadiene and 1,2-dichloroethane in the Daesan Industrial Complex were located at 25.2% and 21.3%, respectively. Inthe case of Ulsan and Yeosu Industrial Complexes, the locations of 1.0×10-6 of 1,3-butadiene were 14.5%and 64.0%, respectively. It implies that the risk of carcinogenesis in the Daesan and Ulsan IndustrialComplexes are greater than the other one. Furthermore, sensitivity analysis results showed thatexposure time (ET) is the most influential factor on risk, with residents who spend more time outdoorsand workers with prolonged exposure to the workplace having a higher risk of carcinogenesis. It iswarranted that more detailed emission sources and further refined risk assessment studies for 1,3-butadiene and 1,2-dichloroethane are required.