As a kind of gas insulation medium, SF6 is widely used in the power industry. Due to its high global warming potential value, the degradation and recycle of SF6 has become a research hotspot in recent years. At present, there have been some achievements in the experimental study on the degradation of SF6, but there is little research on the catalytic degradation of SF6 by metal catalysts. Based on the first-principle, this paper investigated the interaction between SF6 and Ag(1 1 1) and evaluated the possibility of using Ag as a catalyst in SF6 degradation. It is found that SF 6 can interact with Ag(1 1 1) surface with eight initial configurations. After the interaction, the distance between the F atom in the SF6 molecule and the Ag surface is significantly shortened and the S-F bond is elongated. There is a strong charge exchange process between the Ag metal interfaces and SF6 molecule. Ag (1 1 1) transfers electrons of about 1.1e - to the SF6 molecule and the dissociation of SF6 by Ag metal shows a catalytic effect. The related research results provide a theoretical reference for the silver-catalyzed degradation of SF6.