Nickel- and palladium-nickel catalysts supported on silica-alumina have been studied in the simultaneous hydrogenation of naphthalene and toluene. These catalysts were characterised by means of X-ray diffraction, CO chemisorption, temperature-programmed reduction, NH3 temperature-programmed desorption, diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy of adsorbed CO and X-ray photoelectron spectroscopy techniques. All the catalysts studied showed higher initial intrinsic activity in the hydrogenation of toluene than of naphthalene. Regarding the hydrogenation of toluene, the 1Pd-8Ni/SA sample displayed the strongest resistance to deactivation by coke precursors as compared with the Ni-free 1Pd/SA catalyst. For the 1Pd-8Ni catalyst, the characterisation data pointed not only to a high degree of reducibility of nickel but also the greatest exposure of Pd species. Both findings appear to be related to the development of nickel hydrosilicate species at the support interface. Indeed, a better resistance towards deactivation was obtained by Pd incorporation and by increasing Ni-loading.