Layered multi-metallic bulk catalysts NixZnyMoW with different Ni/Zn molar ratios were prepared based on the NiZn-layered hydroxide precursor by co-precipitation method and well characterized by various technologies including XRD, SEM, HRTEM and Raman spectroscopy. HRTEM images illustrated that both the slab sizes and stacking layers of sulfided catalysts were changed with different Zn contents. These catalysts were tested for hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene (4,6-DMDBT) from model diesel. Hydrodesulfurization (HDS) reaction of 4,6-dimethyldibenzothiophene showed that all the catalysts NixZnyMoW with layered structure exhibited high HDS activity and the sulfur content in the model diesel can be reduced from 517 ppm to less than 10 ppm under mild reaction conditions of 3.0 MPa of pressure, 300 degrees C, a LHSV of 9h(-1), and H-2/oil ratio of 800 N cm(3)/cm(3). The catalysts NixZnyMoW have shown much higher specific HDS activity than that of the commercial catalyst CoNiMoW/Al2O3. However, ZnMoW without Ni has shown relatively low activity. The higher HDS activity of NixZnyMoW could be ascribed to high contents of active metals and the layered structure. Meanwhile, the synergism between Ni/Zn and Mo/W plays an important role in achieving the excellent HDS performance of catalysts NixZnyMoW. (C) 2013 Elsevier B.V. All rights reserved.