The international regulation of persistent organic pollutants (POPs) according to the Stockholm convention started in May 2001, and is intended to regulate the production and use of hazardous chemicals on a global scale. PFOS is one of the newly listed emerging POPs and only one of a diverse huge group of perfluoroalkyl substances (PFASs), which are known as a “super set” of chemical tracers that include more than ninety related chemicals. The comprehensive monitoring of PFASs is necessary to develop a reliable understanding of environmental kinetics related to these pollutants. However, the extent of atmospheric pollution by PFASs is still unclear because their distribution and sources are not fully understood. Hence, a reliable analytical method for precisely measuring the levels of PFASs in particulate matter is needed. In this study, in order to investigate the levels of PFASs in atmospheric particles including PM2.5, the use of new sampling equipment was evaluated by obtaining multiple samples of air from a stable meeting room environment. Meanwhile, by simultaneously obtaining samples from a roadside environment, the characteristics of PFASs from two different types of air samples were compared.