This study presents a method to regulate the coverage of gold (Au) atoms on ultrathin PdₓAuᵧ nanosheets (NS) to enhance the direct oxidation of methane (CH₄) to methanol (CH₃OH). The research reveals a volcano-type relationship between the binding strength of hydroxyl radicals (·OH) on the catalyst surface and catalytic performance. The optimized Pd₃Au₁ NS achieved a methanol production rate of 147.8 mmol g⁻¹ h⁻¹ with a selectivity of 98% at 70 °C, making it one of the most efficient catalysts for this reaction. The study shows that the reaction-triggering and reaction-conversion steps in the process are in a trade-off relationship. The performance of the catalyst is influenced by the energy barriers of these steps, with the strength of the M–O bond (M–O ICOHP) serving as a key catalytic descriptor. The study also demonstrates that the Pd₃Au₁ NS exhibits high stability and reusability, with no significant decrease in performance after 10 cycles. The results highlight the importance of controlling Au coverage to achieve optimal catalytic performance in the direct oxidation of methane to methanol. The study provides valuable insights into the reaction mechanisms of DOMM on PdAu alloys and offers a reliable model for developing such alloys with efficient performance.This study presents a method to regulate the coverage of gold (Au) atoms on ultrathin PdₓAuᵧ nanosheets (NS) to enhance the direct oxidation of methane (CH₄) to methanol (CH₃OH). The research reveals a volcano-type relationship between the binding strength of hydroxyl radicals (·OH) on the catalyst surface and catalytic performance. The optimized Pd₃Au₁ NS achieved a methanol production rate of 147.8 mmol g⁻¹ h⁻¹ with a selectivity of 98% at 70 °C, making it one of the most efficient catalysts for this reaction. The study shows that the reaction-triggering and reaction-conversion steps in the process are in a trade-off relationship. The performance of the catalyst is influenced by the energy barriers of these steps, with the strength of the M–O bond (M–O ICOHP) serving as a key catalytic descriptor. The study also demonstrates that the Pd₃Au₁ NS exhibits high stability and reusability, with no significant decrease in performance after 10 cycles. The results highlight the importance of controlling Au coverage to achieve optimal catalytic performance in the direct oxidation of methane to methanol. The study provides valuable insights into the reaction mechanisms of DOMM on PdAu alloys and offers a reliable model for developing such alloys with efficient performance.