A polyoxometalate-templated silver(I) thiolate nanocluster has been synthesized by a one-pot reaction in high yield. This novel and stable nanocluster exhibits a core-shell structure with a Ag67S36 shell and two lacunary Keggin [PW9O34](9-) cores, which is fully characterized by X-ray crystallography, X-ray photoelectron spectroscopy, UV-vis, powder X-ray diffraction, and cyclic voltammetry.