Preschool indoor air quality (IAQ) is believed to be different from elementary school or higher school IAQ and preschool is the first place for social activity. Younger children are more susceptible than higher-grade children and spend more time indoors. The purpose of this study was to compare the indoor air quality by investigating the concentrations of airborne particulates and gaseous materials at preschools in urban and rural locations in Korea. We investigated the concentrations of airborne particulates and gaseous materials in 71 classrooms at 17 Korean preschools. For comparison, outdoor air was sampled simultaneously with indoor air samples. Airborne concentrations of total suspended particulates, respirable particulates, lead, asbestos, total volatile organic compounds and components, formaldehyde, and CO(2) were measured with National Institute for Occupational Safety and Health and/or Environmental Protection Agency analytical methods. The concentration profiles of the investigated pollutants in indoor and urban settings were higher than those in outdoor and rural areas, respectively. The ratios of indoor/outdoor concentrations (I/O) of particulates and gaseous pollutants were characterized in urban and rural preschools. Total dust concentration was highest in urban indoor settings followed by urban outdoor, rural indoor, and rural outdoor locations with an I/O ratio of 1.37 in urban and 1.35 in rural areas. Although I/O ratios of lead were close to 1, lead concentrations were much higher in urban than in rural areas. The I/O ratio of total VOCs was 2.29 in urban and 2.52 in rural areas, with the highest level in urban indoor settings. The I/O ratio of formaldehyde concentrations was higher in rural than in urban areas because the outdoor rural level was much lower than the urban concentration. Since an I/O ratio higher than 1 implies the presence of indoor sources, we concluded that there are many indoor sources in preschools. We confirmed that pollutants in indoor and urban settings were higher than those in outdoor and rural areas, respectively. Preschool children are expected to spend more time inside preschool facilities and therefore to be more exposed to pollutants. As far as we know, preschool IAQ is different from elementary school or higher school IAQ. Also, they are more vulnerable than higher-grade children. We found that the indoor and urban concentration profiles of the studied pollutants in preschools were higher than those in outdoor and rural areas. We believe that our findings may be useful for understanding the potential health effects of exposure and intervention studies in preschools.