Cobalt-niobia catalysts were prepared using different variants of the colloidal sol-gel technique and wetness impregnation. Characterization of these catalysts by XRD, FT-IR, XPS and TEM showed that phases structure as well as superficial composition depended on the preparation route. It was found that niobia exhibits a strong metal support interaction effect and this effect depends on the dimension of the metallic cobalt on the support surface. Reactivity of these catalysts was checked in n-butane hydrogenolysis, a well known structural sensitive reaction. The catalytic tests showed the influence of the catalysts features both on the reaction rate and selectivity.