One-pot reaction of AgSBu^t and AgOAc in the methanol–ethanol–DMF solvent system under room temperature gave a ball-shaped Ag₅₆ cluster and a disc-like Ag₂₀ cluster. The formations of clusters 1 and 2 are templated by an in situ generated S²⁻ ion from the cleavage of the S–C bond of SBu^t and CO₃²⁻ ion from the fixation of atmospheric carbon dioxide, respectively. Interestingly, cluster 1 only emits bright-red light in the solid state at 77 K and is not emissive at room temperature.