Fe-modified ZSM-5 and β zeolites were prepared by adopting liquid ion-exchange method and their catalytic performance was studied in the N2O decomposition reaction. The state of Fe loaded on Fe-zeolites was investigated by means of UV-vis diffuse spectra, infrared spectroscopy, EPR and H2-TPR. The results of IR of hydroxyl stretching and UV-vis investigationSubscript texts indicated that part of the iron-ions was introduced into zeolites at the charge-balancing sites. The results of EPR and H2-TPR investigations showed that the same iron species were loaded on ZSM-5 and β zeolites. However, the results of IR of the perturbed anti-symmetric T-O-T vibrations of iron-ions indicated that different types of ZSM-5 and β zeolites resulted in different distributions of charge-balancing iron cations. The iron-ions could replace Brönsted acid protons at the straight channel wall (α sites), intersection of straight and sinusoidal channels (β sites), and sinusoidal channel wall (γ sites) within the ZSM-5 zeolite. In the case of Fe-β zeolites, iron-ions mainly located in the straight channels. We observed that the catalytic activity of the iron ions located on the α sites of ZSM-5 zeolites was better than those of iron ions located on β and γ sites in N2O direct decomposition, since the former was the most easily reduced from Fe3+to Fe2+in H2. Furthermore, it was found that Fe-β zeolite showed higher catalytic activity than Fe-ZSM-5 zeolite. This difference was attributed to the active sites located almost exclusively in the straight zeolite channels.