Mechanistic and kinetic aspects of the direct decomposition of N₂O over steam-activated Fe-silicalite were investigated by transient experiments in vacuum (N₂O peak pressure of ca. 10 Pa) using the temporal analysis of products (TAP) reactor in the temperature range of 773-848 K. The transient responses of N₂O, N₂, and O₂ obtained upon N₂O decomposition were fitted to different micro-kinetic models. Through model discrimination it was concluded that both free iron sites and iron sites with adsorbed mono-atomic oxygen (*O) species are active for N₂O decomposition. Oxygen formation occurs via decomposition of bi-atomic (*O₂) oxygen species adsorbed over the iron site. This bi-atomic oxygen species originates from another bi-atomic oxygen species (O*O), which is initially formed via interaction of N₂O with iron site possessing mono-atomic oxygen species (*O). Based on our modeling, the recombination of two mono-atomic oxygen (*O) species or direct O2 formation via reaction of N₂O with *O can be excluded as potential reaction pathways yielding gas-phase O₂. The simulation results predict that the overall rate of N₂O decomposition is controlled by regeneration of free iron sites via a multi-step oxygen formation at least below 700 K.