Per- and poly(fluoroalkyl) substances (PFAS) are environmentally persistent pollutants that are of growing concern due to their detrimental effects at ultratrace concentrations (ng·L-1) in human and environmental health. Suitable technologies for on-site ultratrace detection of PFAS do not exist and current methods require complex and specialized equipment, making the monitoring of PFAS in distributed water infrastructures extremely challenging. Herein, we describe amplifying fluorescent polymers (AFPs) that can selectively detect perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) at concentrations of ng·L-1. The AFPs are highly fluorinated and have poly(p-phenylene ethynylene) and polyfluorene backbones bearing pyridine-based selectors that react with acidic PFAS via a proton-transfer reaction. The fluorinated regions within the polymers partition PFAS into polymers, whereas the protonated pyridine units create lower-energy traps for the excitons, and emission from these pyridinium sites results in red-shifting of the fluorescence spectra. The AFPs are evaluated in thin-film and nanoparticle forms and can selectively detect PFAS concentrations of ∼1 ppb and ∼100 ppt, respectively. Both polymer films and nanoparticles are not affected by the type of water, and similar responses to PFAS were found in milliQ water, DI water, and well water. These results demonstrate a promising sensing approach for on-site detection of aqueous PFAS in the ng·L-1 range.