Background: When particles are absorbed into the human body, they penetrate deep into the lungs and interact with the tissues of the body. Heavy metals in PM2.5 can cause various diseases. The main source of PM2.5 emissions in South Korea’s atmosphere has been surveyed to be places of business. Objectives: The concentration of heavy metals in PM2.5 near the Ulsan Industrial Complex was measured and a health risk assessment was performed for residents near the industrial complex for exposure to heavy metals in PM2.5. Methods: Concentrations of heavy metals in PM2.5 were measured at four measurement sites (Ulsan, Mipo, Onsan, Maegok) near the industrial complexes. Heavy metals were analyzed according to the Air Pollution Monitoring Network Installation and Operation Guidelines presented by the National Institute of Environmental Research. Among them, only five substances (Mn, Ni, As, Cd, Cr6+) were targeted. The risk assessment was conducted on inhalation exposure for five age groups, and the excess cancer risk and hazard quotient were calculated. Results: In the risk assessment of exposure to heavy metals in PM2.5, As, Cd, and Cr6+ exceeded the risk tolerance standard of 10–6 for carcinogenic hazards. The highest hazard levels were observed in Onsan and Mipo industrial complexes. In the case of non-carcinogenic hazards, Mn was identified as exceeding the hazard tolerance of 1, and it showed the highest hazard in the Ulsan Industrial Complex. Conclusions: This study presented a detailed health risk from exposure to heavy metals in PM2.5 by industrial complexes located in Ulsan among five age groups. It is expected to be utilized as the basis for preparing damage control and industrial emission reduction measures against PM2.5 exposure at the Ulsan Industrial Complex.