Re/Al2O3 catalysts were prepared from a carbonyl precursor by controlled gas-phase deposition with all conditions accurately monitored by a computer-programmed CVD reactor. The catalysts were made in an inert atmosphere. Growth of the rhenium concentration was studied with different preparation procedures and with different times and temperatures of deposition. Rhenium loading of the catalysts varied between 0.3 and 12.8 wt%. The activity of the catalysts was tested in thiophene hydrodesulfurization reaction and the results suggest good activity in low rhenium loading. The portion of n-butane among the reaction products was high for the catalysts with high rhenium content.