Remediation of soils contaminated by the globally concerning per- and polyfluoroalkyl substances (PFAS) is imperative yet challenging. Herein, we identify a PFAS hyperaccumulator, the herbaceous Oenothera rosea, in soil near a fluorochemical facility and demonstrate root-to-shoot translocation factors of 3.07 - 58.6 for 18 distinct PFAS. Comparative hydroponic/pot experiments using conspecifics from non-polluted areas confirm that hyperaccumulation arises from domestication after prolonged PFAS exposure. Root cell wall pectin and hemicellulose are critical PFAS binding sites, significantly affecting root-to-shoot translocation. Subcellular and transcriptomic analyses reveal that the hyperaccumulating O. rosea undergoes minimal cell wall remodeling under PFAS stress, a signature of adaptive evolution. Life cycle assessment further validates the environmental superiority of an integrated strategy combining O. rosea phytoremediation with biomass pyrolysis for PFAS destruction and biochar production, achieving a net-negative carbon footprint (-17.9 kg CO2/ton soil). Our work provides a comprehensive framework for PFAS remediation, from hyperaccumulator identification to sustainable field application.