Developing sufficiently efficient catalytic systems and effective catalysts for SF6 catalytic degradation holds significant importance for achieving the dual carbon goal. Herein, a highly active CuO/ZnO catalyst has been constructed, facilitating the heterogeneous catalytic synthesis of SF6 into readily recoverable gaseous products. Studies indicate that the CuO/ZnO exhibits abundant oxygen vacancies, thereby demonstrating highly efficient SF6 catalytic degradation. Introducing NH3 into the background gas promotes the generation of Cu sites from CuO, facilitating the de-fluorination decomposition and S element reduction in the catalytic reaction. Solid product characterization revealed that fluorine from SF6 readily solidifies, preventing its release as a highly toxic fluorinated gas. Gas chromatography-mass spectrometer (GC-MS) analysis confirmed over 90% SF6 degradation and the catalytic products contained SO2 with high selectivity, which could be easily removed by alkaline washing. This work provides technical support for future large-scale, environmentally sound SF6 treatment.