Copper staves have been widely applied in large blast furnaces especially those whose inner volumes exceed 2000 m³ due to high cooling capacity. In the past decade, copper staves suffered severe damages in some blast furnaces, which not only shortened their campaign lives, but also caused huge economic losses. In order to make out this phenomenon, the damage mechanism of copper staves was investigated via analyzing the chemical composition, thermal conductivity, metallographic aspects and microstructure in this paper. As a result, the working state was more likely to damage copper staves instead of their materials. At the beginning, the poor quality of the coke and the large bosh angle promoted the development of edge airflow, which intensified the erosion of refractory materials, resulting in the fall-off of slag crusts and damage of cooling water pipes. After repair, the cooling capacity of copper staves still declined, causing the temperature to rise easily; consequently, hydrogen attack happened when the temperature reached 370 °C, which degraded the performance of copper staves. Therefore, copper staves were worn too quickly to form slag crusts, which finally failed under the hydrogen attack and the scouring of the edge airflow at high temperatures.