An ab initio one-pot synthesis of the bimetallic clusters [Au_nAg_44–n(SC₆H₃F₂)₃₀]^4– (abbreviated (AuAg)₄₄; n ≤ 12) is reported. The mixed-metal (AuAg)₄₄ clusters, synthesized with different reactant Au/Ag ratios, exhibit a fractal-like distribution, suggesting that nucleation of the icosahedral core is a fractal growth process. X-ray crystallographic studies provided unambiguous evidence that the doped Au atoms occupy the icosahedral sites and the maximal doping is 12. The number of Au atoms (n) in [Au_nAg_44–n(SR)₃₀]^4– (SR = SC₆H₃F₂) can be continuously tuned from 0 to 12. A three-way correspondence between single-crystal structure, MS, and UV–vis is established, thereby facilitating future identification (finger-printing) of the alloy [Au_nAg_44–n(SR)₃₀]^4– clusters. The temperature, solvent, and temporal effects in the synthesis were also investigated.