Sustainable recovery of critical resources demands catalytic platforms that are efficient, scalable, and low-energy. Contact-electro-catalysis (CEC) provides a promising route, yet conventional powder catalysts suffer from poor dispersion and limited recyclability. Here we introduce a prestressing strategy that regulates molecular ordering and interface charge states, yielding prestressed polytetrafluoroethylene (Ps-PTFE) films. Prestressing aligns dipoles, establishes a built-in electric field, and lowers the barrier for interface charge transfer under ultrasound-assisted, thereby amplifying reactive oxygen species generation. Relative to PTFE powders, Ps-PTFE films boost hydroxyl and superoxide radical production by 243.44 % and 152.29 %, respectively, delivering a 9.6-fold enhancement in catalytic efficiency. This enables highly efficient silver leaching from retired photovoltaic cells, with leaching, reduction, and overall recovery efficiencies of 97.37 %, 98.51 %, and 95.94 %, a 19.93 % improvement over conventional approaches. By establishing an all-film-state CEC platform, this work advances a recyclable, low-carbon, and scalable pathway for critical metal recovery, moving towards the United Nations Sustainable Development Goals.