The treatment of spent cemented carbides using the conventional alkali-acid leaching process results in the generation of hazardous solid waste tungsten leaching residue. This study proposed an alternative process using the alkali-treated tungsten leaching residue (AW-residue) without the acid leaching step, preserving Co in the residue. By using photovoltaic silicon kerf waste (SKW) as a reducing agent, heavy metals (Co, Ni, W, Nb, and Ta) were efficiently extracted from AW-residue and a Co-rich alloy was obtained. The silicothermic reduction process facilitated the recovery of iron group metals (Co, Ni, and Fe) and effectively captured trace refractory metals (W, Ta, and Nb). Phase separation occurred through reduction reaction and viscosity-driven processes between the Co-rich alloy and the slag. Optimal conditions were identified as 20% SKW addition, MgO crucible, and a holding time of 120min, achieving a total recovery yield of 95.5%, with specific yields for Co (97.7%), Ni (97.0%), W (82.5%), Nb (76.3%), and Ta (70.5%). A 20kg pilot-scale experiment confirmed the feasibility of the process, yielding 47.0% Co-rich alloy from AW-residue compared to 48.3% in lab-scale experiment, and producing a harmless slag phase. This environmentally friendly approach promotes sustainable recycling of valuable metals in the tungsten industry. Environmental ImplicationHazardous leaching residue (AW-residue) derived from the hydrometallurgical recycling of spent cemented carbides poses significant environmental hazards, as it cannot be disposed of via landfill or direct smelting. Importantly, the presence of heavy valuable metals (e.g., Co, Ni, W, Nb, and Ta) in the AW-residue leads to substantial resource wastage. A novel strategy for the effective recovery of these valuable metals from AW-residue involves utilizing photovoltaic silicon kerf waste (SKW) as a reducing agent. This approach not only achieves waste disposal using waste, but also minimizes environmental risks.