Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents, which usually serve as the starting point for the preparation of clusters. However, such a process is still far from clear. Herein, we report the controlled synthesis of silver-t-butylthiolate clusters from reactions of polymeric [Ag^tBuS]_n and suitable templates in the presence of solubilizing reagents to offer a detailed look at the mechanism of cluster’s formation. As the provided solubilizing reagents have weak coordination ability, such as O- or N-donating ligands, the obtained polymeric compound retains the linear structure pattern that S and Ag atoms are arranged alternately. When extra templates NO₃⁻ and CO₃²⁻ are applied, the disk-like clusters Ag₁₉ and Ag₂₀ are constructed with the same [Ag^tBuS]₅ circles that may directly cyclize from the linear [Ag^tBuS]_n fragments. In contrast, (EtO)₂PS₂⁻ and (ⁱPrO)₂PS₂⁻ anions have large size and strong coordination ability rendering the structure of the polymer completely fragmented. Thus extremely short [Ag^tBuS]_n pieces with silver ions and solubilizing ligands assemble around the templates V₂O₇⁴⁻ and W₂O₉⁴⁻, leading to the formation of clusters Ag₂₂ and Ag₂₄.