Achieved by introducing defect sites, enhances both the catalytic activity and stability of catalysts. This is crucial for advancing key applications in energy conversion and environmental protection. Here, we introduce a novel Pt-Cu@CeO2/MWCNTs electrocatalyst prepared by dual modulation of the oxygen vacancy anchoring point and the center of the alloying d-band. This catalyst significantly boosts the rate of methanol oxidation. The Pt-Cu@CeO2/MWCNTs catalyst demonstrates a mass activity 3.7 times higher than that of commercial Pt/C, along with exceptional durability. The electron transfer between the PtCu alloy and the oxygen vacancies effectively modulates the d-band center of Pt, leading to a “volcano” relationship between the catalyst’s mass activity and the d-band center. This study advances the development of methanol electrooxidation catalysts by introducing a novel “double enhancement effect” model.