Perfluoroalkyl substances (PFAS) are a class of persistent organic pollutants known as "forever chemicals". Currently, the hydrated electron-based advanced reduction process (ARP) holds promise for the elimination of PFAS. However, the efficiency of ARP is often challenged by an oxygen-rich environment, resulting in the consumption of hydrated electron source materials in exchange for the high PFAS decomposition efficiency. Herein, we developed a ternary system constructed by indole and isopropyl alcohol (IPA), and the addition of IPA significantly enhanced the PFOA degradation and defluorination efficiency in the presence of low-concentration indole (<0.4 mM). Meanwhile, opposite results were obtained with a higher amount of indole (>0.4 mM). Further exploring the molecular mechanism of the reaction system, the addition of IPA played two roles. On one hand, IPA built an anaerobic reaction atmosphere and improved the yield and utilization efficiency of hydrated electrons with a low concentration of indole. On the other hand, IPA suppressed the attraction between indole and PFOA, thus reducing the hydrated electron transfer efficiency, especially with more indole. In general, the indole/PFAS/IPA system significantly improved the PFAS destruction efficiency with a small amount of hydrated electron donors, which provided new insights for development of simple and efficient techniques for the treatment of PFAS-contaminated wastewater.