In the * state (without adsorption), both systems show similar Bader charges on the Au(surface) (0.13), but the Au(staple) in [Au25(SCH2COOH)17] -has a significantly lower charge (0.03) compared to [Au25(SCH2CH3)17] -(0.11). The lower charge on Au(staple) in hydrophilic cluster suggests a lower electron density, which could promote better interaction with protons facilitating proton transfer and enhancing the hydrogen evolution. When hydrogen is adsorbed (*H state), both systems exhibit negative charges on the Au sites, indicating electron transfer from H to Au. However, the Au(staple) site in [Au25(SCH2CH3)17] -holds a higher negative charge (-0.04) compared to [Au25(SCH2COOH)17] -(-0.02), suggesting a stronger electron interaction with hydrogen. This stronger interaction likely hinders H2 desorption in the hydrophobic cluster, raising the energy barrier for H2 release. In contrast, the more balanced electron distribution in hydrophilic cluster allows for easier H2 desorption, contributing to its superior HER performance. In the *COOH state, a crucial intermediate for CO2RR, the Au(staple) in [Au25(SCH2CH3)17] -shows a more negative charge (-0.12) than in [Au25(SCH2COOH)17] -(-0.08). This indicates that the hydrophobic cluster better stabilizes the *COOH intermediate by receiving more electrons from the adsorbed species. This enhanced stabilization lowers the energy barrier for *COOH reduction to *CO, explaining the superior CO₂RR performance of [Au25(SCH2CH3)17] -. Conversely, the less negative charge on Au(staple) in hydrophilic cluster results in weaker stabilization of *COOH, leading to a higher energy barrier for this reduction step and contributes to its lower CO2RR efficiency.