The design and development of hydrodesulfurization (HDS) catalysts with superior catalytic activity for the conversion of refractory organosulfur compounds has been highly desirable, but still remains challenging in the petroleum processing field. Herein, a series of Pt-triggered Ni 2P/Al 2O 3 catalysts were fabricated and examined for 4,6-dimethyldibenzothiophene (4,6-DMDBT) HDS. The loading of Pt strengthened the interaction between the Pt and Ni 2P and promoted the hydrogen atoms overflowing to the Ni 2P surface due to the lower electronegativity of Pt compared to Ni, thereby enhancing the number of Lewis and Brønsted acid sites and facilitating the prehydrogenation and isomerization pathways, and thereafter substantially boosting the HDS performances of Pt-Ni 2P/Al 2O 3 catalysts. Therein, 5%Pt-Ni 2P/Al 2O 3 exhibited the optimal HDS performance with 97.1% 4,6-DMDBT conversion, remarkably higher than that of Ni 2P/Al 2O 3 (25.6%) and the-state-of-the-art catalysts reported in literature due to its moderate acidity and temperate interaction between Pt and Ni 2P.