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Doping of metal nanoclusters is an effective strategy for tailoring their functionalities for specific applications. To gain fundamental insight into the doping mechanism, it is of critical importance to have access to a series of correlated bimetal nanoclusters with different doping levels and further reveal the successive transformations. Herein, we report asymmetric doping of Ag into an Au₂₁ nanocluster to form a series of new Au/Ag bimetal nanoclusters and the effects of doping on the evolution of size, structure, and properties based upon X-ray crystallography and optical spectroscopy analyses. The asymmetric doping discovered in the series reveals two important rules. First, the heteroatom doping-induced kernel transformation mechanism is revealed, explaining the successive conversions from Au₂₁(S-Adm)₁₅ with an incomplete cuboctahedral kernel to Au₂₀Ag₁(S-Adm)₁₅ with a complete cuboctahedral Au₁₂Ag₁ …