Abstract <p>The Pd-Pt/mesoporous-γ-Al₂O₃(Pd-Pt/MA) catalyst with bimetallic and mesoporous characteristics was successfully synthesized via the impregnation method. Using dibenzothiophene (DBT) as a model compound, its catalytic performance and sulfur tolerance in hydrodesulfurization (HDS) reactions were systematically investigated. Results demonstrate that the electronic structure of the active sites is effectively modulated by an electronic cooperative effect between Pd and Pt, which weakens the strong adsorption of sulfur species and significantly enhances the catalyst’s sulfur tolerance. The catalyst remained stable after ten hours of operation, achieving a DBT conversion rate of 88.39% in the HDS reaction. Moreover, it maintained high activity and favorable catalytic performance after three regeneration cycles. Structural characterization and molecular dynamics simulations revealed that the mesoporous structure improves mass transfer efficiency while suppressing coking and side reactions. The primary HDS pathway over the mesoporous catalyst is direct desulfurization. The stability of active sites is largely dependent on the desorption of H₂S and the free diffusion of excess hydrogen from the bimetallic-support interface. This work provides new perspectives for designing highly efficient, sulfur-tolerant hydrodesulfurization catalysts.</p> Graphical abstract <p></p>