Recently, perfluoroalkyl substances (PFASs) have received great attention from both academia and the industry due to their persistence and health risks. Here, we developed a simple ternary self-assembled micelle composite, consisting of a photosensitive substance (indole acetic acid, IAA), cationic surfactant (cetyltrimethylammonium bromide), and contaminant (PFAS). Owing to the rapid hydrated electron transfer from IAA to the PFAS in the micelle, the PFAS degradation and defluorination were greatly enhanced even under ambient conditions. After 2.5 h UV irradiation, the perfluorooctanoic acid (PFOA) concentration decreased from 10 mg L-1 to ∼60 ng L-1, which is below the drinking water health advisory level of the United States Environmental Protection Agency for the combined concentration of PFOA and perfluorooctane sulfonate (70 ng L-1). Meanwhile, the dissolved organic carbon content of the reaction solution was also reduced to ∼3 mg L-1 due to the quick settlement and automatic separation of the micelle. Furthermore, the newly developed composite was also adaptable to a wide pH range (pH 4-8), attributing to the barrier created by the ternary micelle system. This novel self-assembly method is expected to directly treat industrial PFAS-containing wastewater or PFAS-enriched concentrates derived from adsorption processes. The conceptually new advanced reduction technique represents a major breakthrough toward PFAS rapid destruction and efficient usage of hydrated electrons and might also shed light on other environmental applications.