<p>An increasing number of ore tailings generated from the metal ore beneficiation and smelting are expected to be reused in the near future; however, traditional treatments lack efficient secondary utilization of ore materials. Herein, polymetallic ore tailing is firstly recycled into SiO₂-based nanofillers through a plasma-assisted ball milling technology, and the obtained SiO₂ is successfully applied in the PVdF-HFP-based solid electrolyte in Li metal batteries. It is found that the trace amounts of element Sn in ore tailing would be successfully introduced into the SiO₂, and synthesized Sn-doped SiO₂ shows a lamellar structure with good crystallinity and rich oxygen vacancies. The addition of Sn-doped SiO₂ can improve the ionic conductivity, mechanical properties, and thermal stability of SSE, achieving low electrochemical polarization and high reversibility in the solid-state symmetrical Li cells. Manufactured solid-state NCM622||Li full cell exhibits good charge capability, stable cyclic property, and rate capability under room and high temperatures. This work is the first attempt to realize the recycling of ore tailings into SiO₂ nanofillers in advanced solid-state Li metal batteries, which may supply a new sight of the reusing treatment and applications of ore tailings in the field of electrochemical energy storage.</p>