Per- and polyfluoroalkyl substances (PFASs) are a class of synthetic chemicals of concern that exhibit extreme persistence within the environment and possess physicochemical properties that are resistant to targeted degradation. Comprising substantial concentrations of PFASs, aqueous film-forming foams (AFFFs) present a major exposure pathway to the environment having been applied to land at firefighting-training sites globally for decades. This has led to significant contamination of environmental media. Herein, we demonstrate that mechanochemical destruction (MCD) is an effective method for the destruction of PFASs in an AFFF concentrate and an authentic sample of PFAS-contaminated soil derived from a decommissioned firefighting training facility. Both targeted analysis and non-targeted analysis were used in this study to evaluate the degradation of PFASs in complex substrates during MCD treatment. Destruction efficiencies of target PFAS subgroups ranged from 99.88% to 100%. The only additive employed for MCD treatment was quartz sand, which was used only for the liquid AFFF sample, with no additives required for the destruction of PFASs in the contaminated soil. This confirms the viability of MCD for both the remediation of PFAS-contaminated land and the destruction of stockpiled AFFFs.