Unsupported catalysts based on nickel, cobalt, tungsten, and molybdenum were prepared by sulphurization of Ni, Co, W, and Mo oxides. All catalysts were tested in hydrodesulphurization of dibenzothiophene reaction. The best activity was attained with a sample based on W (5.64 x 10(16) molecules/s m(2)). The best selectivity for biphenyl (70.14 %) was achieved with Ni17S18. Materials were characterized by X-ray diffraction and surface area measurements. Reaction network for hydrodesulphurization (HDS) of dibenzotiophene (DBT) by direct desulphurization pathway (DDS) and hydrogenating pathway (HYD) to produce biphenyl (BP) and cyclohexyl-benzene (CHB). nH(2) = hydrogen excess at 3.378 MPa, dihydrodibenzotiophene (DHDBT), tetrahydrodibenzothiophene (THDBT), hexahydrodibenzothiophene (HHDBT), hydrogen sulphide (H2S). Ni17S18 as a yield of 12.03 % THDBT, 17.83 % CHB, and 70.14 % BP.