Background removal in X-ray photoelectron spectroscopy (XPS) spectra was carried out in Co–Mo hydrodesulfurization (HDS) catalysts supported alumina using traditional and recent methods. The sulfidation extent, expressed by the XPS area ratio AMo3d-MoS2/AMo3d-Total, which is a fundamental parameter in the performance of a hydrodesulfurization catalyst, was obtained using different methodologies. The methods include the use of the background active approach, in which the background is optimized during peak-fitting. The method allows for the use of several types of backgrounds, which proved crucial for fitting the Mo 3d-S 2s and the S 2p–Si 2p regions. Both regions contain two overlapped elements, making fundamental a distinction between them. In these cases, a slope background subtraction was used in conjunction with the Shirley-Vegh-Salvi-Castle (SVSC) method to have a clear distinction between the different strengths of backgrounds arising from the overlapped peaks Mo 3d-S 2s and S 2p–Si 2p. From the resulting fitting, the relative percentage (% rel.) of each species present in Mo and S in the catalyst CoMoAl was obtained. The results were compared with those obtained using the static (traditional) approach. With these results, the sulfidation extent, an important parameter in the performance of the HDS catalyst was determined.Adolfo-Romero Galarza thanks Consejo Nacional de Ciencia y Tecnologia (CONACyT), Mexico for their postdoctoral fellowship (ID. 1908/2010C ) . We acknowledge financial support from Direccion General de Asuntos del Personal Academico ( DGAPA) Mexico, UNAM , project PAPIIT-IN-113015 . The authors appreciate the support provided by Gustavo Gomez-Sosa (CINVESTAV-Qro.) for the acquisition of the XPS data and Alberto Herrera-Gómez (CINVESTAV-Unidad Queretaro, Mexico) for engaging in useful discussion regarding the spectra fitting and for providing computer program AANALYZER version 1.2.