The direct oxidative esterification of methacrolein (MAL) has drawn considerable attention as a promising route to produce methyl methacrylate (MMA). Here, we report a kinetics strategy to identify the active sites of Au catalyst for its disentanglement of geometric and electronic effects on this reaction. A series of Al2O3 and CeO2 supported Au catalysts are prepared by urea deposition–precipitation method, whose particle sizes are tailored by changing the vacuum-drying temperature. Their catalytic activity is correlated with Au particle size based on a crystal structure modelling, in which the Au edge site is identified as the main active site. The reduction in the valence electron population of Au 5d states facilitates the adsorption of MAL, thus the positive core-level shift of Au 4f levels for each support gives rise to a higher production of MMA. This kinetics strategy could be extended to the design of other metal catalysts for this reaction.