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Abstract The determination of gas phase thermochemical properties of per‐ and polyfluoroalkyl substances (PFAS) is central to understanding the long‐range transport behavior of PFAS in the atmosphere. Prior gas‐phase studies have reported the properties of perfluorinated sulfonic acid (PFOS) and perfluorinated octanoic acid (PFOA). Here, this study reports the gas phase enthalpies of formation of short‐ and long‐chain PFAS and their precursor molecules determined using density functional theory (DFT) andab initioapproaches. Two density functionals, twoab initiomethods and an empirical method were used to compute enthalpies of formation with the total atomization approach and an isogyric reaction. The performance of the computational methods employed in this work were validated against the experimental enthalpies of linear alkanoic acids and perfluoroalkanes. The gas‐phase determinations will be useful for future studies of PFAS in the atmosphere, and the methodological choices will be helpful in the study of other PFAS.