Exposure to air pollution affects human activity and health. Particularly, in Asian countries, the influence of particulate matter on humans has received wide attention. However, there is still a lack of research about the effects of particulate matter on human outdoor activities and mental health. Therefore, we aimed to explore the association between exposure to particulate matter with a diameter of less than 10 µm (PM10) and outdoor activity along with mental health in South Korea where issues caused by particulate matter increasingly have social and economic impacts. We examined this relationship by combining the physical and habitual factors of approximately 100,000 people in 2015 from the Korean National Health Survey. To measure each individual’s exposure to particulate matter, we computed the total hours exposed to a high PM10 concentration (>80 μg/m3) in a given district one month before the survey was conducted. After dividing all districts into six groups according to the exposed level of the high PM10, we applied the propensity score-weighting method to control for observable background characteristics. We then estimated the impact of the high PM10 on outdoor activity and mental health between the weighted individuals in each group. Our main findings suggest that the impact of PM10 on outdoor activity and stress shows an inverted-U shaped function, which is counterintuitive. Specifically, both outdoor activity and stress levels tend to be worsened when the exposure time to a high PM10 (>80 μg/m3) was more than 20 h. Related policy implications are discussed.