Structural transformations of nanoclusters provide a platform to tune their properties and understand the fundamental science due to their intimate structure–property correlation. Here, we present an alkynyl ligand-exchange induced growth of atomically precise silver(I) clusters, which are particularly of interest because of their luminescence response at room temperature. SCXRD and UV-vis map out the growth steps of the cluster from [Ag₃₂S₃(CCBu^t)₂₃]³⁺ featuring a pseudo-D_3h concave Ag₃₂S₃ to [Ag₄₅S₆(CCPhBr)₃₂]⁺ with a pseudo-O_h core–shell Ag₉S₆@Ag₂₄@Ag₁₂, which is driven by a thermodynamic route under the disruption of ligands. To our knowledge, the findings in this work establish the first example of ligand-exchange as a versatile tool for tuning the size and luminescence of semiconductor silver(I) clusters.