Abstract: High-value recycling and utilization of spent CIGS photovoltaic cells are crucial to the development of new energy and circular economy industries. A complete recycling route for spent CIGS photovoltaic cells has not been established, and high-value metals in the cells are recovered in relatively limited forms. A standardized recycling process is constructed, and a combined recovery technology is determined, which includes alkaline leaching of CIGS powder, nitric acid leaching of metal ions, solvent extraction, and hydrothermal synthesis of In₂O₃, Ga₂O₃ and MOF materials. Under the optimized conditions: sodium hydroxide concentration of 0.85 mol/L, reaction time of 2 h, temperature of 80 ℃, and liquid-to-solid ratio of 10 mL/g, CIGS powder purity is maintained at 98.36%, and the corresponding recovery rate is kept at 95.15%. In the acid leaching stage, copper, indium and gallium leaching rates reach 99.46%, 96.09% and 97.95% respectively at nitric acid concentration of 4.4 mol/L, reaction duration of 3.5 h, reaction temperature of 75 ℃ and liquid-solid ratio of 14 mL/g. Metal ions are separated by adopting P204 and Lix984 extractants, and the separation efficiencies of copper, indium and gallium are measured as 99.36%, 95.23% and 96.05%. Purified metal solutions are applied to material preparation, and In₂O₃, Ga₂O₃ and copper trimellitate with distinctive microscopic morphologies are successfully fabricated. All synthesized products possess extensive application potential. The established technical route is characterized by superior separation performance, complete technical chain and high added value of recycled products, and reliable technical basis is offered for resource regeneration of waste CIGS photovoltaic cells.