However, in this study, we strategically synthesized three distinct Cu NCs using a meticulously designed one-pot reduction method. The synthesized NCs include [Cu11(PTT)9(PPh3)6] 2+ (Cu11PTT) (PTT: p-toluenethiolate) and [Cu11(ABT)9(PPh3)6] 2+ (Cu11ABT) (ABT: m-aminobenzethiolate) NCs, which share a similar structural architecture but differ in their thiolate ligand systems, and [Cu18H2(PTT)15(PPh3)6] (Cu18PTT) NC, which features the same PTT ligand as Cu11PTT but adopts a distinct structural architecture. These variations were achieved by precisely controlling the reduction conditions during the synthesis process. Although both Cu₁₁ NCs share the same geometry, differences in their ligands significantly impact cuprophilic interactions within the clusters, directly affecting the core confinement. In contrast, Cu18PTT demonstrates how even with the same PTT ligand, adjustments in the reduction conditions can lead to a rearrangement of the core's structural architecture. This rearrangement is also driven by modified cuprophilic interactions, emphasizing the critical role these interactions play in defining the core geometry. The alteration in cuprophilic interactions has profound implications for the catalytic properties of these NCs. Changes in core length and structural arrangement directly affect the active catalytic sites, thereby influencing the efficacy and selectivity of the catalytic processes. Furthermore, the nature of the surface ligands plays a pivotal role in dictating product selectivity, highlighting the importance of ligand choice in tailoring catalytic performance. Thus, this study not only demonstrates a precise strategy for designing Cu NCs with tailored structural architectures by controlling their reduction conditions but also elucidates the significant impact of structural variations and surface ligand modifications on catalytic behavior. The findings also underscore how subtle changes in synthesis parameters and ligand systems can lead to optimized catalytic applications with enhanced product selectivity.