Gold cyanidation barren solution is rich in copper/zinc cyano-complexes and possesses high recovery value. However, existing processes typically require the conversion of copper cyano-complexes into compound precipitates prior to smelting recovery, resulting in a relatively complex flowsheet and high energy consumption. To address this issue, a coupled process integrating ferrous precipitation and zero-valent aluminum reduction is proposed to achieve barren solution purification and valuable resource recovery. In this process, zinc cyano-complexes are first selectively precipitated by ferrous ions for zinc recovery; then, copper cyano-complexes are reduced by zero-valent aluminum assisted by ferrous ions to recover elemental copper; finally, ferrocyanide is precipitated by ferrous mass ions to recover Prussian blue. The results indicate that after treatment by this method, the total zinc concentration in the solution decreases from 1.95 g/L to 0.01 g/L, total copper mass concentration from 2.25 g/L to 0.03 g/L, and total cyanide mass concentration from 10.30 g/L to 0.20 g/L. The obtained zinc sludge contains over 22% zinc, the copper powder contains over 90% elemental copper, and the iron sludge contains over 50% Prussian blue. Economic analysis shows that the comprehensive reagent cost is approximately 78.4 CNY/m³ of barren solution, while the direct revenue from the produced elemental copper sludge is about 200 CNY/m³. This method provides a technical reference for the resource recycling and utilization of cyanide gold leaching barren solution.