The first observation of luminescence from a structurally well-defined Ag(2)S molecular nanocluster is reported. Reaction of AgSBu(t)/AgBF(4) with N(2)H(4) in methanol affords the tetracationic cluster [Ag(62)S(13)(SBu(t))(32)](BF(4))(4), which has a core-shell configuration. The 14 silver(I) centers of the [Ag(14)S(13)] core are in a face-centered cubic arrangement with each edge bridged by a S(2-) ligand; the core is further connected to the [Ag(48)(SBu(t))(32)] shell via both Ag-S bonds and Ag···Ag interactions. This novel cluster displays intense red emission in both the solid state and solution at room temperature.