In the context of Au25 NCs, the choice and nature of ligands are critical factors that significantly influence their stability and catalytic performance. Ligands act as the outer protective layers, not only preventing aggregation and stabilizing the nanocluster, but also modulating its electronic properties and surface chemistry. The thiol-based ligands, in particular, are widely used due to their strong S-metal bonds, which provide high stability and a straightforward preparation strategy. However, beyond the stabilization effect, the intrinsic properties of the ligands-such as their hydrophilicity or hydrophobicity-can profoundly affect the nanocluster's interaction with reactants and its overall electrocatalytic activity. For instance, investigated the impact of different ligands on the HER performance and found that the 3-mercapto-1propanesulfonic acid (MPS) protected Au25 NC achieved a rate constant of 121,000 s -1 at an overpotential of 0.7 V, which was 11 times higher than that of the 1-hexanethiolate (C6S) protected Au25, highlighting the profound influence of ligand hydrophilicity on catalytic efficiency. Moreover, a recent work by Yoo et al. has showed that the introduction of hydrophobic ligands in a silver nanocluster Ag25 can enhance the CO2 reduction activity, achieving a Faradaic efficiency for CO (FECO) of over 90% and a partial current density (jCO) as high as -240 mA cm -2 in a gas-fed membrane electrode assembly device. Despite these experimental progresses, the atomic-level understanding and elucidation of the specific effects of hydrophilic versus hydrophobic ligands on the electrocatalytic performance of atomically precise NCs have been lacking. This uncertainty underscores the urgent importance of systematic investigation into how the ligand properties influence these catalytic processes. Particularly, understanding these interactions is crucial for further optimizing the performance of Au25 NCs and could also provide valuable insights into the rational design of nanocluster-based electrocatalysts for sustainable energy applications.