Hydrodesulfurization (HDS) reactions of radioactive 35S-labeled dibenzothiophene ([35S]DBT) were carried out over a variety of Cr/Al2O3 with 5.5–33.3 wt.% CrO3 and over promoted Me-Cr/Al2O3 (Me/Cr = 0.4, 0.6; Me = Ni, Co and Cu) catalysts at temperatures in the range of 300–380°C and under a reaction pressure of 5.0 MPa. The HDS activity of Cr/Al2O3 catalysts increased with increasing Cr loadings to 33.3 wt.% CrO3. Moreover, both HDS and hydrogenation (HYD) activities of Cr/Al2O3 catalysts were enhanced with the addition of Ni and Co. In contrast, adding Cu to Cr/Al2O3 catalyst decreased its catalytic activity inversely. Further, the results obtained from the HDS reaction of 35S-labeled dibenzothiophene indicated that the amount of labile sulfur increased on adding Ni and Co to Cr/Al2O3 catalysts whereas it decreased on adding Cu. It is suggested, therefore, that the addition of Ni and Co weakens the strength of the chromium–sulfur bond on the sulfided Cr/Al2O3 catalyst, and brings about increases in amount of labile sulfur and in catalytic activity of the Cr catalyst.