Unsupported catalysts have attracted much attention for high activity in comparison with the traditional supported catalyst. Meanwhile, the clear structure of unsupported catalysts is helpful for the recognition of active phase for conducting the industry production. The NiMoW unsupported catalyst was prepared by hydrothermal synthesis and characterized by BET, XRD and HRTEM. The effects of naphthalene, quinoline and H2S on the hydrodesulfurization reactivity of dibenzothiophene (DBT) were investigated in both a batch autoclave and a continuous 10 ml fixed bed micro-reactor over NiMoW and supported catalyst for comparison. The results showed that the hydrogenation reaction and the hydrogenolysis reaction occurred on different active sites. For supported catalyst, the inhibition was relatively weaker, and the inhibition of the hydrodesulfurization pathway was much higher than the direct desulfurization pathway. Although unsupported catalyst was very sensitive to quinoline and H2S in this experiment, the HDS ratio on the unsupported catalyst was maintained at a high level above 99.7%, which is attributed to the very high active site density of unsupported catalysts.