AbstractMicrokinetic simulations have been carried out to describe the partial oxidation of methane over silica‐supported molybdena and vanadia. The objective of this study was to formulate a physically reasonable reaction network to capture the basic aspects of the surface catalytic chemistry and to use this network to link methane oxidation kinetics with the kinetics observed for the oxidation of subsequent gaseous products, i.e., methanol, formaldehyde, and carbon monoxide. The most abundant reactive intermediates on the catalyst surface are suggested to be oxygen and hydroxyl groups. This reaction network successfully predicts the catalytic activities, selectivities, activation energies, and reaction orders observed over silica‐supported molybdena and vanadia; and the microkinetic model also semiquantitatively explains the kinetic trends for related catalyst systems and is consistent with surface bonding energetics reported in the literature over various oxide catalysts. The microkinetic reaction network properly reduces to the more simple macrokinetic model reported previously for methane partial oxidat