The first macrocycle-based high-nuclearity nanocluster [Ag(20)(S(t)Bu)(10)(CF(3)COO)(2)](8+) in complex 1, with a sandwich-like structure constructed by bilevel inversion Ag(5)S(5) pentagrams and an interlayer Ag(10) ring, has been obtained. Structure analysis indicates that Cl(-) acts as an anion template to direct the formation of 1. In addition, the photoluminescent property of complex 1 is also investigated.