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(CCBut)23]3+ featuring a pseudo-D3h concave Ag32S3 to [Ag45S6(CCPhBr)32]+ with a pseudo-Oh 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.