A series of Ni-rich bimetallic phosphides incorporating different metals were successfully prepared by initial wetness impregnation, followed by temperature-programmed reduction. Catalyst characterization indicates that the bulk structure and physical properties maintained after adding 2.5 mol% another metal on Ni2P. Electron transfer from the second metal to Ni was found on Mo0.05Ni1.95P, Co0.05Ni1.95P, and Fe0.05Ni1.95P, except on W0.05Ni1.95P. Simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene (DBT) over phosphides and a commercial metal sulfide were studied at 320-380 degrees C, 3 MPa, weight hourly space velocity of 6 h(-1), and H-2/feed ratio of 500:1. Metal phosphides show higher HON of quinoline and the same HDS of dibenzothiophene activities than that of a commercial catalyst at 380 degrees C. Mo0.05Ni1.95P shows the best performance and lowest N and S content adsorbed on the catalyst due to the active M(2) sites. HDS conversion and product selectivities are seriously impacted by the adsorption of N-containing compounds on active sites of catalysts. Increasing temperature to 360 degrees C or/and decreasing N content to less than 1000 ppm quinoline in the feed are suggested to obtain simultaneous efficient removal of N and S. (C) 2014 Elsevier B.V. All rights reserved.