The global exponential increases in annual photovoltaic (PV) installations and the resultant waste PV cells are an increasingly serious concern. How to dispose of and value-added recycling of these end-of-life PV cells has become an important issue in view of environmental or economic views. Herein, a potential sustainable development idea was put forward to recover silicon materials from stripped discarded photovoltaic modules based on wet leaching and nano-metal catalyzed etching to prepare porous silicon/carbon (PSi/Li/N@C) composite materials for the anode of lithium-ion batteries (LIBs). The results show that alkali/acid leaching can effectively remove the main impurities and obtain high purity silicon (∼99.86%). The resulting PSi/Li/N@C composite exhibits a high capacity of 685.2 mA h g⁻¹ after 100 cycles at 2000 mA g⁻¹. This work provides a potential application prospect and a new strategy for the value-added recycling of discarded PV cells.