In this study, the concentrations of particulate matter 10 μm or less in diameter (PM10) and carbon dioxide (CO2) were measured in 100 underground subway stations, and the potential health risks of PM10, and environmental factors affecting these concentrations were analyzed. The concentrations were measured from May 2014 to September 2015 in stations along Seoul Metro lines 1–4. There were significantly different PM10 concentrations among the underground subway stations along lines 1, 2, 3, and 4. The PM10 concentrations were associated with the CO2 concentrations, construction years, station depths, and numbers of passengers. The underground PM10 concentrations were significantly higher than the outdoor PM10 concentrations. In addition, the PM10 concentrations were higher in the stations that were constructed in the 1970s than in those constructed after the 1970s. The PM10 and CO2 concentrations varied significantly, depending on the construction year and number of passengers. The hazard quotient is higher than the acceptable level of 1.0 μg kg−1 day for children, indicating that they are at risk of exposure to unsafe PM10 levels when travelling by the metro. Therefore, stricter management may be necessary for the stations constructed in the 1970s as well as those with higher numbers of passengers.