Unsupported molybdenum disulfide catalysts were synthesized from ammonium tetrathiomolybdate with chitosan, hexadecylammonium and Triton X100 as structural agents by leaching of MoS2/Al2O3 and MoS2/C/Al2O3 catalyst supports with HF acid and covering of "FeS" seeds by the MoS2 shell. Activation of the solids was performed under the H2S/H-2 flow or by the decomposition of precursors in the presence of a hydrocarbon solvent in an autoclave reactor with varied H-2 pressure. X-ray diffraction, N-2 adsorption, temperature-programmed reduction, X-ray photoelectron spectroscopy and transmission electron microscopy techniques were used to characterize their structure and morphology. The nature of organic additives and activation conditions affect the surface area, pore size distribution, and morphological characteristics of MoS2 particles. Hydrodesulfurization of dibenzothiophene was performed in an autoclave reactor over unsupported MoS(2)based catalysts. The catalytic behavior of bulk MoS2 catalysts showed that the hydrogenation pathway prevailed over the direct desulfurization pathway. Higher HYD/DDS selectivity for dibenzothiophene hydrogenation was observed with the bulk molybdenum disulfide catalyst formed by etching of the MoS2/Al2O3 catalyst support. Unsupported Mo sulfide catalysts exhibited high hydrogenation activity in dibenzothiophene hydrodesulfurization and, therefore, might find wide applications in hydroprocessing of heavy feed and co-hydro treating of petroleum fractions and plant oils.