Due to the implementation of more stringent specifications in sulfur content for gasoline , a deep understanding of the active phase of Co-Mo/Al2O3 catalysts is necessary to the development of hydrodesulphurization (HDS) catalysts. A series of Co-Mo/Al2O3 HDS catalysts with different metal loading were studied by laser Raman spectra. The existence form and the content of the active component of the catalyst were obtained by Raman spectra. The result shows that the percentage of characteristic Raman bands 940 cm-1 correlates linearly with the HDS selectivity, which can be used as an experimental evidence for developing industrial selective HDS catalysts. Raman spectra of sulfided catalysts show that the bands of oxidic catalysts at 839 and 940 cm-1 disappeared, and simultaneously, the bands of Mo—S at 372 and 408 cm-1 emerged, which indicate that the oxidic sample is sulfided completely.