Electronic structure of catalysts has a great influence on their performance and understanding these functional mechanism of electrons quantitatively in the molecular-scale is of importance to design efficient catalysts. Herein we study the regulation of electronic effect on gold catalysts by using the atmospheric oxidation of alcohols as probe reaction. Binding ligands results in a turnover frequency increase (6197 h-1 at 220 oC) closing to the best gold catalyst (twinning structure) reported before. Combining results from X-ray absorption spectroscopy along with a series of in-situ studies, we reveal that electronic-rich processes could provide additional active sites for the reactants under solvent free gas-phase conditions. Theoretical calculations clarify the regularity that gold surface with lower work function is favorable to the thermal oxidation process. It provides a pathway for us to rational design highly efficient precious metal catalysts in the gas-phase reaction.