The results revealed that the Au-S interface is unstable under the applied electrochemical reduction potential, and the hydrophilic [Au25(SCH2COOH)17] - dictates faster kinetics for the stripping of -SR ligand. Moreover, in the acidic environment, the hydrophilic Au25 NCs also exhibit superior HER performance than the hydrophobic one due to the enhanced proton transfer and hydrogen evolution facilitated by the hydrophilic environment. Conversely, in the alkaline condition, the hydrophobic Au25 NCs show better CO2RR activity by promoting the adsorption and stabilization of CO2 intermediates while minimizing the water interference around the reaction interface. These insights provide a deeper understanding of how the ligand environments affect the electrocatalytic activities of Au25 nanoclusters and offer valuable guidance for the rational design of promising nanocatalysts for electrocatalytic applications.