Direct decomposition of N 2 O was investigated using simulated and real industrial gas stream coming from an adipic acid plant. Two different kinds of catalysts were studied: (i) LaB 1−x B′ x O 3 and CaB 1−x Cu x O 3 (B=Mn, Fe and B′=Cu, Ni) perovskites (PVKs) and (ii) supported PVKs (10 or 20wt.%) on γ-Al 2 O 3 and CeO 2 –ZrO 2 . The structural modifications induced by the composition of PVK samples affect the catalytic performances: mixed oxide formation in CaMn 0.7 Cu 0.3 O 3 samples allows to reach the highest values of N 2 O conversion while the effect of PVK phases is more controversial. The importance of copper on catalytic activities is confirmed by the investigation on CaMn 1−x Cu x O 3 samples. The best results were obtained with a CaMn 0.6 Cu 0.4 O 3 catalyst calcined at 700°C for 5h, in which the presence of copper maximises the Ca 3 CuMnO 6 phase formation. The increase in Cu-content produces a large segregation of CuO despite PVK formation. The best catalyst was tested using industrial gas stream, showing good stability also in the presence of H 2 O and O 2 (8%v/v ) after 1400h on-stream. To increase surface area, Cu-containing PVKs were deposed on γ-Al 2 O 3 and CeO 2 –ZrO 2 , and this latter has been recognised as the best support. Indeed, the activity of the PVKs supported on ceria–zirconia is comparable to and even better than that of the bulk catalysts. A possible explanation regards the support contribution in terms of activity and/or promotion of O 2 mobility which enhances the overall activity of the catalyst.