Polytetrafluoroethylene (PTFE) is among the most inert poly- and perfluoroalkyl substances (PFASs) and its degradation under mild conditions remains underdeveloped. We report a supercapacitor-assisted electrophotocatalysis, incorporating the strength of both electrochemical and photochemical energy, for the efficient defluorination of PTFE and other PFASs at low temperatures. CBZ6 worked as a photoreductant for injecting electrons into the inert carbon-fluorine bond, whereas the supercapacitor enabled the generation of the catalytically active species via an electrophotochemical process. Furthermore, the utilization of sunlight as the light source and supercapacitor as the electrical energy source makes the reaction portable and enables its outdoor applications.