The mechanism of direct N₂O decomposition over Fe-ZSM-5 and Fe-silicate was studied in the temporal analysis of products (TAP) reactor in the temperature range of 773-848 K at a peak N₂O pressure of ca. 10 Pa. Several kinetic models based on elementary reaction steps were evaluated to describe the transient responses of the reactant and products. Classical models considering oxygen formation via recombination of two adsorbed monoatomic oxygen species (*-O + *-O —> O₂ + 2*) or via reaction of N₂O with adsorbed monoatomic oxygen species (N₂O + *-O —> O₂ + N₂ + *) failed to describe the experimental data. The best description was obtained considering the reaction scheme proposed by Heyden et al. (J. Phys. Chem. B 2005, 109, 1857) on the basis of DFT calculations. N₂O decomposes over free iron sites (*) as well as over iron sites with adsorbed monoatomic oxygen species (*-O). The latter reaction originates adsorbed biatomic oxygen species followed by its transformation to another biatomic oxygen species, which ultimately desorbs as gas-phase O₂. In line with previous works, our results confirm that the direct N₂O decomposition is controlled by pathways leading to O₂. Our kinetic model excellently described transient data over Fe-silicalite and Fe-ZSM-5 zeolites possessing markedly different iron species. This finding strongly suggests that the reaction mechanism is not influenced by the iron constitution. The TAP-derived model was extrapolated to a wide range of N₂O partial pressures (0.01-15 kPa) and temperatures (473-873 K) to evaluate its predictive potential of steady-state performance. Our model correctly predicts the relative activities of two Fe-FMI catalysts, but it overestimates the absolute catalytic activity for N₂O decomposition.