The [AuxAg16‐x(SAdm)8(Dppe)2] nanocluster with aggregation‐induced emission (AIE) was synthesized from a non‐fluorescent [Au9Ag12(SAdm)4(Dppm)6Cl6](SbF6)3 nanocluster via a ligand‐exchange engineering (Dppe=1,2‐Bis(diphenylphosphino)ethane, Dppm=Bis(diphenylphosphino)methane, HSAdm=1‐Adamantanethiol). The nanocluster has a Au‐doped icosahedral AuxAg13‐x core, capped by two Ag(SR)3, one Ag(SR)2 and two Dppe ligands. By changing the achiral Dppe ligand into a chiral dbpb ligand ((2S,3S)‐(‐)‐Bis(diphenylphosphino)butane or (2R,3R)‐(+)‐2,3‐Bis(diphenylphosphino)butane), chiral nanoclusters are obtained. ESI‐MS and UV‐vis spectroscopy were performed to track the reaction. This work provides guidance for the construction of new clusters by etching clusters with multidentate phosphine ligands.