This study investigated perfluoroalkyl substances (PFASs) in multimedia environments to confirm the effects of emission sources of PFASs and to elucidate their spatial distribution. The highest PFAS levels were detected from the samples of air (272.30 pg/m3) and surface water (36.54 ng/L) in an industrial complex area, meanwhile high PFAS levels were found from the samples of soil (8.80 ng/g) and sediment (84.98 ng/g) in urban areas and near wastewater treatment plants (WWTPs). Perfluorobutane sulfonate (PFBS) was primarily detected in water, influent and effluent, whereas long chain perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) were dominant in dust, soil, sediment and sludge. While PFBS and neutral PFASs were dominant in air, PFCAs were primarily detected in plant and fish. The specific distribution patterns of PFASs in each matrix showed the influences of surrounding environments and different physicochemical characteristics of each congener. These findings suggest that the industrial complex and WWTP might be major emission sources to air and aquatic environments, respectively. This is the first study in which 6 neutral and 13 ionic PFASs were investigated simultaneously for nine different matrices in multimedia environments, and also it would be a good model study for future assessment of PFASs.