Herein, we report a new method to synthesize molecular gold nanoclusters (AuNCs) stabilized by phosphine (PR₃) and di-N-heterocyclic carbene (di-NHC) ligands. The interaction of di-NHC gold(I) complexes, with the general formula [(di-NHC)Au₂Cl₂] with well-known [Au₁₁(PPh₃)₈Cl₂]Cl clusters provides three new classes of AuNCs through a controllable reaction sequence. The synthesis involves an initial ligand metathesis reaction to produce [Au₁₁(di-NHC)(PPh₃)₆Cl₂]⁺ (type 1 clusters), followed by a thermally induced rearrangement/metal complex addition with the formation of Au₁₃ clusters [Au₁₃(di-NHC)₂(PPh₃)₄Cl₄]⁺ (type 2 clusters). Finally, an additional metathesis process yields [Au₁₃(di-NHC)₃(PPh₃)₃Cl₃]²⁺ (type 3 clusters). The electronic and steric properties of the employed di-NHC ligand affect the product distribution, leading to the isolation and full characterization of different clusters as the main product. A type 3 cluster has been also structurally characterized and was preliminarily found to be strongly emissive in solution.