The atmosphere is the first medium containing hazardous compounds entering the living environment. Metropolitan areas contain many industrial complex areas with high emissions of volatile organic compounds (VOCs), and consequently also large-scale exposure groups. As respiration is the most important part of the human exposure pathway, the atmosphere should be treated with greater importance than other media. It is therefore very important to monitor the emission of hazardous air pollutants (HAPs) and measure the concentration of VOCs in the atmosphere of such areas. It is essential to establish basic measures in order to protect public health as part of overall national safety management. This study utilized the national air pollution monitoring network data from Seoul, Incheon, and Gyeonggi, and investigated the differences in risk levels for humans considering various factors of the receptors, including gender and age. A total of 13 VOCs were categorized into carcinogens and noncarcinogens for risk assessment. The carcinogens 1,3-butadiene and benzene demonstrated a high level of cancer risk, ranging between 10−4 and 10−6, respectively. Noncarcinogens did not exceed Hazard Quotient (HQ) 1 in any area. The results will serve as important references for managing urban air environments and setting air quality standards.