Perfluoroalkyl substances (PFASs) were measured in air and dust from cars, homes, offices, and school classrooms in Ireland, along with drinking water from homes and offices. Perfluorooctanoic acid (PFOA) dominated air and drinking water, while perfluorobutane sulfonate (PFBS) dominated dust. This is the first report of PFOA, perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), PFBS, and perfluorononanoic acid (PFNA) in air inside cars and school classrooms. PFOS concentrations in classroom air exceeded significantly (p ≤ 0.05) those in homes. Atmospheric concentrations of PFOA, PFNA, and methyl perfluorooctane sulfonamido ethanol (MeFOSE) (p ≤ 0.05) were significantly higher in cars containing child car seats than in cars without. PFOS, PFOA, PFBS, and PFHxS were all detected frequently in drinking water, but concentrations of PFASs were low, and although ΣPFASs were 64 ng/L in one bottled water sample, this fell below a Swedish Action Level of 90 ng ΣPFASs/L. The Irish population's exposure to PFOS and PFOA via non-dietary sources is well below estimates of dietary exposure elsewhere in Europe. Moreover, even under a high-end exposure scenario, it falls below the European Food Safety Authority's (EFSA) provisional tolerable weekly intakes for PFOS and PFOA.