A set of Cu-ZSM-5 samples (Si/Al = 25) was synthesized by wetness impregnation, aqueous phase ion exchange and solid-state ion exchange, SSIE. Copper(II) acetate was used as precursor during both wetness impregnation and aqueous phase ion exchange to prepare excessively-exchanged samples (Le. Cu/Al > 1), whereas SSIE was carried out by sublimating copper(I) chloride. Additionally, a Cu-ZSM-5 sample with extremely low Al content (Si/Al = 500) was prepared by impregnation. The samples were tested in the catalytic decomposition of N2O, with the aim of studying possible effects of the preparation technique on the isothermal oscillatory behavior of the reaction rate in a series of tests carried out by varying both the temperature and the residence time. The SSIE sample led to a non-oscillating system, whereas the highest Cu content samples prepared by the two aqueous procedures exhibited clear oscillations of the reaction rate. The Cu-ZSM-5 with Si/Al = 500 was quite inactive, but, surprisingly, gave rise to oscillations of both unconverted N2O and produced O-2 concentrations at the reactor outlet. A combined IR spectroscopy and H-2-TPR study showed the role of oligomeric CuxOy species with extra-lattice oxygen close to the Al atoms on the observed oscillations. Such species are much more abundant in the samples prepared by either impregnation or ion-exchange, when Cu/Al > 1. In contrast, the sample prepared by SSIE resulted to be rich in Cu+ isolated species, active for the reaction, but not inducing oscillation.