Per- and polyfluoroalkyl substances (PFASs) are synthetic contaminants found in drinking groundwater sources and a wide variety of consumer products. Because of their adverse environmental and human health effects, remediation of these persistent compounds has attracted significant recent attention. To shed mechanistic insight into their remediation, we present the first ab initio study of PFAS degradation via hydrated electrons - a configuration that has not been considered in previous studies up to this point. To capture these complex dynamical effects, we harness ab initio Molecular Dynamics (AIMD) simulations to probe the reactivities of perfluorooctanoic (PFOA) and perfluorooctane sulfonic acid (PFOS) with hydrated electrons in explicit water. We complement our AIMD calculations with advanced metadynamics sampling techniques to compute free energy profiles and detailed statistical analyses of PFOA/PFOS dynamics. While our calculations show that the activation barrier for C-F bond dissociation in PFOS is three times larger than PFOA, all the computed free energy barriers are still relatively low, resulting in a diffusion-limited process. We discuss our results in the context of recent studies on PFAS degradation with hydrated electrons to give insight into the most efficient remediation strategies for these contaminants. Most importantly, we show that the degradation of PFASs with hydrated electrons is markedly different than that of excess electrons/charges, a common (but largely incomplete) approach used in several earlier computational studies.