The radiolysis route is applied to synthesize nickel catalysts deposited on titanium dioxide. The TPR profile of radiation-induced Ni/TiO2 catalyst indicates a more complete reduction of the irradiated catalysts compared to the conventionally H-2-reduced one. When tested in the benzene hydrogenation, the radiolytic Ni/TiO2 exhibits catalytic properties with higher efficiency than the H-2-reduced catalyst. This observation is assigned to the presence of intermetallic Ni-Ti compounds (Ni2.66Ti1.33 and Ni3Ti) evidenced by XRD. In contrast, the calcined and H-2-reduced catalyst contains predominantly the oxidized Ni5TiO7 phase, where the nickel is in strong interaction with the support. The TEM observations show highly dispersed nickel.