These experimental results have well corroborated our computational predictions, confirming that the hydrophilic ligand-protected Au25 NCs are more effective for HER in acidic environments due to enhanced proton transfer facilitated by the hydrophilic ligands. Conversely, the hydrophobic ligand-protected Au25 NCs demonstrate superior CO2RR activity in alkaline conditions by promoting adsorption of CO2RR intermediates and minimizing the water interference, thereby enhancing CO2 reduction efficiency. This alignment between computational and experimental findings underscores the critical role of ligand properties in tuning the electrocatalytic performance of atomically precise metal NCs, providing valuable insights for the rational ligand design of nanocatalysts in sustainable energy applications.