The hydrodesulfurization (HDS) of dibenzothiophene (DBT) was studied at 300 °C, 4.8 MPa H2 and 35 kPa H2S in the presence of 0 to 6 kPa 2-methylpyridine and 2-methylpiperidine. 2-Methylpyridine suppressed the hydrogenation pathway by a factor of 6 to 30, depending on its partial pressure, and moderately inhibited the direct desulfurization pathway of the HDS of DBT (by a factor of 2 or less). 2-Methylpiperidine suppressed the hydrogenation by a factor of 10 to 50 but promoted the direct desulfurization of DBT at low partial pressures of 2-methylpiperidine. Both pathways were inhibited at high concentrations of 2-methylpiperidine. Structural and electronic factors may account for the promoting effect of 2-methylpiperidin