Bulk MoP catalyst was synthesized by temperature-programmed reduction of the corresponding oxidic catalyst precursors, which were prepared with three different P sources, namely H3PO4, (NH4)3PO4, and NH4H2PO4, in hydrogen at different temperatures (723, 773, 873, and 973 K, respectively). The samples were characterized by X-ray diffraction and temperature programmed reduction methods. And the catalytic activities of these samples were prepared at 773 K and evaluated in thiophene hydrodesulfurization under the atmospheric pressure. The crystalline phase of MoP can be formed with these three P sources at different temperatures. For the three catalysts being prepared at 773 K with different P sources, all exhibited thiophene hydrodesulfurization catalytic activities with similar reaction trends. Among them, the catalytic activity of MoP prepared with NH4H2PO4 as the P source was the best. After hydrodesulfurization reaction, the bulk structure of MoP catalyst phase stayed unchanged for all of these tested catalysts.