Electrolyte additives play an important role in suppressing lithium dendrites through tailoring the composition/property of the SEI, however lacking of additives can achieve high performances both in ether and carbonate electrolytes hinders further enhancement of the high voltage lithium-metal batteries. Here, lithium perchlorate (LiClO4) has been presented as an excellent additive to meet the above requirements. An optimized chemical composition of SEI can be achieved through the formation of ionic association. Our results indicate that the LiClO4 behaves like a catalyst, which promotes LiTFSI to form a better SEI to inhibit further reaction. Superior coulombic efficiencies and cycling performances were obtained both in ether and carbonate electrolytes. This study paves a new pathway for designing bi-soluble additives for safe lithium metal batteries.