A new approach to kinetic modeling of heterogeneous-homogeneous radical processes of the partial oxidation of low paraffins over oxide catalysts is suggested. It is based on the elucidation of gas phase and heterogeneous reactions taking part in the overall process and on the correlation between their thermochemistry and kinetics. The model calculations explain : (1) the magnitudes of the reaction rates at different temperatures; (2) the mechanism of catalysts re-oxidation; (3) the influence of the addition of peroxides on the rate of oxidative coupling of methane.