Ag/Ni electrical contact material is one of the most promising contact materials to replace Ag/CdO because of its excellent electrical and thermal conductivity. However, the poor arc corrosion resistance and melt welding resistance of Ag/Ni electrical contact materials limit their development. In this article, an interfacial model of Re-, In-, and Nb-doped Ag/Ni is established based on the first principle. It has been found that doping can effectively enhance the interfacial stability and bonding strength of Ag/Ni. Furthermore, it is predicted that the performance of Re-doped Ag/Ni contact materials will be optimal. The Ag/Ni electrical contact materials were prepared by combining the high-energy ball milling method and powder metallurgy method. They were then tested for wettability and electrical contact properties. It was found that after doping, the arc energy, arc duration, contact resistance, and welding force decreased. In addition, the Re-doped contact materials showed the most significant improvement. The arc ion sputtering deposition model of Ag/Ni electrical contact materials was finally established to uncover the mechanism behind the arc erosion of Ag/Ni contact materials.