Non-classical Ni/Nb2O5 catalysts [Ni introduced by the simple (SIM) or EDTA-double impregnation (DIM) methods] were prepared by aqueous hydrazine reduction at 353 K. Their structural and surface properties were investigated by XRD, TEM, XPS techniques, and by H-2-TPR, H-2- or O-2-adsorption and isopropanol decomposition measurements. The results obtained confirmed that niobia is a typical SMSI oxide. Indeed, the hydrazine reduced the support and not the supported Ni2+ ions due to the SMSI effect. Reduction proceeded only in case of a layer of Ni2+ ions weakly bonded to a sub-layer of Ni2+ ions strongly attached to the support. This was achieved by stepwise impregnation with the nickel precursor. A very strong nickel-niobia interaction plays a crucial role in the passivation phenomenon of nickel active sites towards hydrogen or in gas phase hydrogenation of benzene. The SMSI effect was in parallel studied on classical catalysts prepared by the SIM or DIM method for comparison. (c) 2006 Elsevier B.V. All rights reserved.