Here we report a neutral fullerene-like core-shell homosilver Ag@Ag nanocluster that is fully protected by an achiral bidentate thiolate ligand (9,12-dimercapto-1,2--carborane, CBHSH), which crystallizes in centrosymmetric space group 3̅. Continuous Cu doping in the dodecahedral shell first induced symmetry breaking to generate chiral Ag@AgCu (6 ≥ ≥ 2) containing two acetonitrile ligands in space group 222, and then produced symmetric all-thiolated Ag@AgCu (20 ≥ ≥ 13) in the higher space group 3̅. The selectively copper-doped Ag@AgCu (6 ≥ ≥ 2) cluster has its structure reorganized to a lower symmetry that shows chiroptical activity. Moreover, structural distortion of Ag@AgCu (6 ≥ ≥ 2) further expanded in chiral -/-propylene oxide, which induced a more prominent core-based CD response. This work revealed a novel mechanism of chirality generation at the atomic level through asymmetric shell-doping of metal nanoclusters, which provides new insight into the origin of chirality in inorganic nanostructures.